On the synthesis of functionalized porphyrins and porphyrin conjugates: Via β-aminoporphyrins

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Tsivadze, New J. Chem., 2016, DOI: 10.1039/C5NJ03247D.

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On the synthesis of functionalized porphyrins and porphyrin

conjugates via β-aminoporphyrins

Inna A. Abdulaeva,^a,bKirill P. Birin,^b,* Julien Michalak,^aAnthony Romieu,^a,cChristine Stern,^aAlla

Bessmertnykh-Lemeune,^aRoger Guilard,^a,* Yulia G. Gorbunova^b,dand Aslan Yu. Tsivadze^b,d

Received 00th January 20xx,

Accepted 00th January 20xx

DOI: 10.1039/x0xx00000x

The synthesis of functionalized porphyrins and conjugates from meso-tetraarylporphyrins through the acylation and the

oxidation of β-aminoporphyrins was investigated. 2,3-Dioxochlorins were prepared by the oxidation of a variety of

β-aminoporphyrins and subsequently used in a condensation reaction with functionalized aromatic aldehydes and

ammonium acetate to form β-functionalized porphyrins bearing a fused imidazole ring. Under optimized experimental

conditions both reactions tolerate various functional groups and afford the products in an appropriate overall yield. The

mildness and usefulness of this methodology is illustrated by several examples including the synthesis of porphyrins bearing

receptor groups and water-soluble conjugates.

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hydrophilic porphyrins soluble under physiological conditions,

as well as conjugates of porphyrins with other molecules

exhibiting dual functions required in biomedicine and

Introduction

Porphyrin chemistry, inspired by natural processes, has

evolved into vast field of knowledge unlocking the

photovoltaic devices. We have studied the preparation of

these modular systems from available meso-

a

applications of tetrapyrrolic compounds in solar energy

transformation, cancer photodymanic therapy, catalysis,

development of novel functional materials and so forth.^1-10

However, there is still a key difference between natural and

synthetic porphyrins. Indeed, the majority of naturally

occurring porphyrins does not contain meso-substituents and

the utilization of meso-substituted porphyrins as “natural”

mimics and the optimal structure of the tetrapyrrolic

molecules studied nowadays is questionable. This irrational

modelling origins from the difficulties of the synthesis of

tetraarylporphyrins 2H-1 focusing our studies on the mild

procedures tolerated by different functional groups (Scheme

1). In this regard, mono β-aminoporphyrins 2H-2 seem to be

attractive intermediate compounds because of their ready

availability from meso-tetraarylporphyrins 2H-1 by using

nitration,^19-30followed by the reduction of the nitro group.^21,31-

36

Scheme 1 briefly summarizes different synthetic approaches to

modular porphyrins from -aminoporphyrins 2H-2. Commonly

used acylation reaction (Scheme 1, Path A) does not tolerate

many functional groups at the meso-aryl substituents because

acyl halides are highly reactive towards nucleophilic

β

-

substituted porphyrins due to the complexity of preparing

3,4-disubstituted pyrrole starting materials. Therefore, the

development of synthetic routes leading to functionalized

β

-

porphyrins has become a priority in porphyrin synthesis.^11-14

Futhermore, functionalization of the outer periphery of the

porphyrin macrocycle was recognized in the last decades as a

versatile synthetic approach to β-

substituted derivatives.^15-18

substitution.^37-41In addition,

a flexible character of the

alkylamide spacer could be somewhat inconvenient in part

because of undesirable intramolecular interactions of the

functional groups with the central metal ion of the porphyrin

complex.

Among synthetic porphyrins designed for applications, there is

a broad series of modular systems comprising of a tetrapyrrolic

macrocycle, a suitable linker and a functional moiety. These

compounds are useful for the development of drugs,

supported catalytic systems, chemosensors, biomarkers,

Recently, the Buchwald-Hartwig amination reaction was

investigated as an alternative route to β-substituted porphyrin

conjugates (Scheme 1, Path B).^42-44The reported systems were

prepared by using of the catalytic reactions of nickel (II)

-aminoporphyrinates with aromatic halides. It is noteworthy

that highly acidic conditions (H₂SO₄) are needed for the

demetallation of these conjugates that may result in their

decomposition.

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O

HO₂C

NH

SO₃H

Ar

Ar HN

NH

N

Ar

HN

N

HN

Ar

2H-3

A

Ar

O

Ar

NH₂

HN

N

O

NH

N

NH

N

NH

N

NH

N

D

2 steps

Ar

HN

N

2H-1

2H-2

Ar

functional moiety

Ar

B

C

=

Ar

N

Ar HN

N

NH

N

NH

N

Ar

HN

Ar

Scheme 1. Conventional strategies for the β-functionalization of meso-tetraarylporphyrins 2H-1 through β-aminoporphyrins 2H-2 (solid arrays) and synthetic approaches to water-

soluble porphyrin conjugates 2H-3 (dotted arrays).

According to the third approach (Scheme 1, Path C), the acetate (AMAC) and 2,3-dioxochlorins obtained by photo-

oxidation of -aminoporphyrins 2H-2 to 2,3-dioxochlorins oxidation of -aminoporphyrins 2H-2 followed by hydrolysis of

followed by their condensation with o-phenylenediamines the resultant keto-imino chlorin. These reactions proceed

yields a rigid quinoxaline linker between a porphyrin and a under mild conditions and tolerate functional groups attached

functional moiety.^21,31-36The structural features of the to the benzaldehyde. The rigid character of the imidazole

functional subunit defined by the substitution pattern of the spacer prevents the intramolecular interactions between the

starting o-phenylenediamines are a serious drawback for the porphyrinic macrocycle and the functional moiety that is

design of modular systems. Furthermore, physico-chemical attractive for the preparation of supported catalytic systems,

properties of these π-extended porphyrin systems significantly chemosensors or metal-organic framework materials.

differ from those of their tetrapyrrolic precursors, thereby Surprisingly, this strategy was only used for the elaboration of

limiting their utility for the preparation of functional molecular several hydrophobic porphyrin conjugates for photophysical

systems.

studies.^46-52Accordingly, only behavior of 2,3-dioxo-

Another attractive approach was reported in late 90^thby 5,10,15,20-tetraarylchlorins with mesityl and 3,5-di-tert-

Crossley’s group and is still scarcely studied.⁴⁵According to this butylphenyl substituents in the condensation reaction were

strategy, a fused imidazole moiety serves as a linker in studied and the scope of this synthetic pathway remains

modular molecules (Scheme 1, Path D). These conjugates are unclear by now.

prepared by condensation of benzaldehydes, ammonium

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ARTICLE

Ar

NH₂

Ar

M

Ar

NO₂

Ar

M

NO₂

NH

N

NH

N

ii

iii

i

Ar

HN

Ar

Ar 2H-1(a-g)

Cu-4(a-f) (68-84%)

Ni-4g (88%)

Ar 2H-4(a-g) (74-95%)

2H-2(a-g)

Ar

Ni-1g

Ar = Tol (a), Mes (b), 4-Br-C₆H₄(c), 4-MeCO₂-C₆H₄(d), 4-(EtO)₂P(O)-C₆H₄(e), 2,6-Cl₂-C₆H₃(f), C₆F₅(g)

Scheme 2. Synthesis of β-aminoporphyrins 2H-2a-g. General conditions and reagents: i. Cu(NO₃)₂, acetic or succinic anhydride (see ESI, Table 1); ii. Cu-4a,c,d,e: H₂SO₄,

CH₂Cl₂, r.t.; Cu-4b,f and Ni-4g: H₂SO₄/TFA, r.t. or reflux; iii. SnCl₂∙2H₂O, HCl, CH₂Cl₂, r.t.

In the context of our ongoing projects in sensing, imaging and temperature whereas H₂SO₄/TFA mixture is needed for the

material chemistry, we are investigating viable synthetic decomplexation of porphyrinates Cu-4b,f and Ni-4g bearing

pathways to functionalized porphyrins and porphyrin ortho-substituted aryl groups at the macrocycle ring. All the

conjugates from meso-tetraarylporphyrins 2H-1 bearing obtained 2-nitroporphyrins 2H-4a-g were then reduced with a

different

-functionalization strategy. Herein, the results on the CH₂Cl₂to give the crude 2-aminoporphyrins 2H-2a-g (Scheme

synthesis of -aminoporphyrins 2H-2 and their conjugation 2).³²It should be also noted that the stability of the free-base

with functional moieties by using alkylamide and imidazole -aminoporphyrins 2H-2a-g is highly dependent on the meso-

spacers (Scheme 1, Path A and D) are reported. In particular, aryl substituents. Compounds 2H-2e,g bearing electron-

we have explored the oxidation of wide range of withdrawing diethoxyphosphoryl or fluorine groups are more

substituents

at

the

meso-positions

via mixture of tin(II) chloride dihydrate and concentrated HCl in

β

a

-aminoporphyrins 2H-2 to 2,3-dioxochlorins and the stable and can be isolated in a pure form by column

condensation of these diones with aromatic aldehydes in the chromatography over silica while other 2-aminoporphyrins 2H-

presence of AMAC. We also illustrate the usefulness of this 2a-d,f should used in the next step without purification and

methodology for the preparation of water-soluble porphyrin directly after preparation due to their sensitivity to photo-

conjugates 2H-3

.

oxidation^53,54and heating^55,56. This instability is a key factor

limiting their utility for further elaboration of functionalized

porphyrins and corresponding conjugates.

Results and discussion

β

-aminoporphyrins and their tranformations.

O

The nitration reaction was chosen as an entry point for the

functionalization of the periphery of meso-tetraarylporphyrins

(Scheme 2). This reaction has been extensively studied and

NH₂

Ar

HN

CO₂H

NH

N

NH

N

succinic anhydride

CH₂Cl₂, reflux

Ar

experimental procedures for selective mono-β-nitration were

HN

developed for a wide variety of porphyrins bearing meso-aryl

substituents at the macrocycle periphery.^19-29Among different

synthetic procedures developed for the nitration of meso-

tetraarylporphyrins, the treatment of free base porphyrins

with copper (II) nitrate in the presence of acetic anhydride

seems to be the most convenient and general procedure.¹⁹In

fact, the reactivity of each porphyrin in 2H-1 series under

these conditions was somewhat different but after

optimization of the reagent amount, the temperature and the

reaction time, all -nitroporphyrins Cu-4a-f were obtained in

good to high yields (Scheme 2, 68-84%) (see ESI, Table S1).

Pentafluorophenyl substituted porphyrin 2H-1g was less

reactive under the studied conditions and yields only copper

(II) porphyrinate Cu-1g in quantitative yield. Therefore,

nitration of this compound was carried out by using the

reaction of nickel (II) derivative Ni-1g with copper (II) nitrate in

the presence of succinic anhydride.

Ar

2H-2e

Ar

2H-5e

Ar

O

Ar = 4-(EtO)₂P(O)C₆H₄

O

NH

N

Ar

+

N

HN

Ar

2H-6e

Scheme 3. Acylation of 2-aminoporphyrin 2H-2e

.

Going further, both acylation and alkylation of

-aminoporphyrins 2H-2 were explored. -Aminoporphyrin

2H-2e bearing electron-withdrawing diethoxyphosphoryl

substituents slowly reacted with succinic anhydride affording

target product 2H-5e in 74% yield with 2,3-dioxochlorin 2H-6e

(16%) formed through the competing oxidation reaction

The demetallation of copper 2-nitroporphyrinates under acidic

conditions was also widely studied.²¹Accordingly,

demetallation of complexes Cu-4a,c,d,e by concentrated

sulfuric acid smoothly proceeds in CH₂Cl₂solution at room

(Scheme

3).

However,

the

aminolysis

of

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(2-pyridyl)methylbromide and ethyl bromoacetate by amine oxidation

Journal Name

with

benzeneselenic

anhydride.⁵⁸

These

2H-2e in the presence of different bases (K₂CO₃, K₂HPO₄, DIEA) porpholactones have also been obtained by oxidation of meso-

– 59

led to inseparable mixtures of starting compound, alkylamines tetraaryl-2,3-dihydroxy-chlorins with MnO₄.

and oxidation products.

In this regard, the photo-oxidation of -aminoporphyrins to electron deficient 2-aminoporphyrin 2H-2g bearing meso-

2,3-dioxochlorins followed by Debus-Radziszewski pentafluorophenyl substituents resulted in a complicated

In agreement with these results, the photo-oxidation by air of

condensation⁴⁵is of particular interest for the preparation of mixture of products which were not identified.

porphyrin conjugates (Scheme 1, Path D). Unfortunately, Thus, our data show that strong electron-withdrawing groups

experimental conditions for both reactions were only briefly attached to the porphyrin ring facilitate the oxidative

described in the first report⁴⁵and in later publications.^49,51

degradation of porphyrin-α-diones. In contrast, photo-

oxidation of sterically hindered amines 2H-2b,f having two

o-alkyl or o-chloro substituents yielded the target porphyrin-α-

diones 2H-6b,f in good yields indicating that steric factors are

less important for the reaction course.

Ar

O

N

NH

N

Ar

NH₂

To overcome the limitations observed in the photo-oxidation

of 2-aminoporphyrins 2H-2e,g, we explored different synthetic

approaches to porphyrin-α-diones by using 2H-6e as a model

compound. Firstly, we studied the oxidation of amine 2H-2e by

air in the presence of acetic acid (AcOH, 10 equiv) in CH₂Cl₂at

room temperature because as mentioned above porphyrin-α-

dione 2H-6e was obtained as a side product when reacting

amine 2H-2e with succinic anhydride (Scheme 3). According to

MALDI-TOF mass analysis of the reaction mixture, amine 2H-2e

was fully stable under these conditions even after 48 h of

stirring. Its selective oxidation to porphyrin-α-dione 2H-6e was

observed when anhydrous sodium acetate (10 equiv.) was

added to the reaction mixture. However, the reaction was

slow and did not go to completion even after 4 days of

vigorous stirring. The better result was obtained when this

compound was oxidized with the Dess–Martin periodinane

(DMP)⁵⁸following the two-step procedure reported by

Promarak and Burn.⁵⁷According to this protocol, the target

product 2H-6e was obtained in 99% yield through stirring of

arylamine 2H-2e with DMP (1.2 equiv.) in CH₂Cl₂for 1 h in the

dark followed by addition of diluted HCl to hydrolyse any imine

intermediates that may have been formed during this

oxidation. Porphyrin-α-dione 2H-6e was purified by column

chromatography over alumina using degassed air-free eluents.

HN

i

NH

N

Ar

ii

2H-6(a-f) (60-99%)

HN

Ar

O

Ar

2H-2(a-g)

O

NH

N

Ar

HN

Ar = Tol (a), Mes (b), 4-BrC₆H₄(c), 4-MeCO₂C₆H₄(d),

4-(EtO)₂P(O)C₆H₄(e), 2,6-Cl₂C₆H₃(f), C₆F₅(g)

Ar

2H-7e (33%)

Scheme 4. Photooxidation of

β-aminoporphyrins 2H-2a-g. Reagents and

conditions: i. 2H-6a-d,f: O₂, hν, H₂O, SiO₂, CH₂Cl_2,r.t., 2 h; 2H-2e: i. a) DMP,

CH₂Cl₂, r.t., 1 h; b) aq. HCl, r.t. ii. 2H-2e: a) O₂, hν, H₂O, SiO₂, CH₂Cl_2,r.t., 2 h; b)

stirring, r.t., 12 h.

Our studies demonstrate that the outcome of the photo-

oxidation of -aminoporphyrins 2H-2 by air in the presence of

hydrated silica in CH₂Cl₂is strongly influenced by the nature of

the substituents at the periphery of the porphyrin macrocycle

(Scheme 4). After

2 h of irradiation by visible light,

2,3-dioxochlorins were obtained in good yields from

-aminoporphyrins bearing p-tolyl- (2H-2a), mesityl- (2H-2b),

p-bromophenyl- (2H-2c), p-methylcarboxyphenyl- (2H-2d) and

2,6-dichlorophenyl

photo-oxidation of p-diethoxyphosphoryl substituted amine

2H-2e was more complicated and gave mixture of

(2H-2f) substituents. Surprisingly, the

Condensation of porphyrin-α-diones with substituted

aromatic aldehydes.

a

With porphyrin-α-diones in hands, we next investigated the

Debus-Radziszewski condensation. In the preliminary

experiments the reaction of porphyrin-α-dione 2H-6a with

inseparable products. We believe that a low yield of the

porphyrin-α-dione 2H-6e, detected in the reaction mixture by

MALDI-TOF mass analysis, is due to a competition between the

oxidation of the 2-aminoporphyrin 2H-2e and the porphyrin-α-

aldehyde

8

was conducted according to literature

procedures^45,49,51involving stoichiometric ratio of carbonyl

compounds in the presence of an excess of AMAC (100 equiv)

in CHCl₃/AcOH mixture (1:1, v/v) heated at reflux (Scheme 5).

However, the product was obtained only in 25% yield (Table 1,

entry 1). Therefore, the reaction was thoroughly investigated

in order to obtain satisfying isolated product yields and reveal

the influence of substituents on the reaction course. The

results for the tolyl derivative 2H-6a are summarized in Table

1.

dione 2H-6e ^45,57

Indeed, when stirring of the reaction mixture

.

was prolonged for 8 h after switching the light off, another

product was detected in the reaction mixture using MALDI-TOF

mass spectroscopy (m/z 1177). This compound was obtained

in 35% yield by column chromatography on alumina and

identified as the 2-oxa-3-oxochlorin 2H-7e by using NMR, IR

spectroscopy and ESI mass spectrometry (see ESI). It is

noteworthy that 2-oxa-3-oxochlorins were never obtained in

the photo-oxidation of 2-aminoporphyrins by air but were

already

prepared

reacting

these

amines

with

m-chloroperbenzoic acid⁴⁵or by the porphyrin-α-dione

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aldehydes

8

-

13 (5 equiv) and AMAC (100 equiv) were

Table 1. Synthesis of imidazoporphyrin 2H-14a by the condensation of 2,3-dioxo-

5,10,15,20-tetra(4-tolyl)chlorin (2H-6a) and 4-bromobenzaldehyde

8.

performed in CHCl₃/TFA mixture (99:1, v/v) at reflux (Scheme

5). The product yield was found to be dependent on the

substituent pattern of both carbonyl reagents. For instance,

p-tolyl- and mesityl-substituted 2,3-dioxochlorins 2H-6a and

Entry

8 (equiv)

Acid (CHCl₃/Acid ratio)

AcOH (1:1)

Time (h)

Yield (%)

1

2

3

4

5

6

7

8

1

2

6

25

60

86

90

0

AcOH (1:1)

2

AcOH (9:1)

6

2H-6b reacted with aldehyde

8 and AMAC affording

5

AcOH (9:1)

6

imidazoporphyrins 2H-14a and 2H-14b in 90% and 64% yields,

respectively. This significant difference in the product yields

demonstrates the strong influence of the porphyrin-α-dione

structure on the reaction course. Nevertheless, under

optimized conditions both porphyrin-α-diones 2H-6a and 2H-

6b reacted smoothly with a series of aromatic aldehydes 8-13

always providing target products 2H-14-19 in good yields (48-

90%). More interestingly, the condensation of 2,3-

dioxochlorins 2H-6c-f bearing functional groups at the

periphery of the macrocycle proceeded without negatively

impacting on the product yield.

20

5

AcOH (9:1)

6

TFA (99:1)

3.5

1

TFA (99:1)

2

TFA (99:1)

0

Reaction conditions: 2H-6a (0.05 mmol), benzaldehyde 8 and AMAC (100 equiv)

were refluxed in 10 mL of CHCl₃/acid mixture. TFA = trifluoroacetic acid.

R

Ar

O

HN

N

O

NH

N

NH

N

R-CHO (8-13), NH₄OAc

Ar

acid, CHCl_3,reflux

According to these reactions, we prepared valuable

compounds with reactive functional groups suitable for further

modifications (2H-14 and 2H-15) and with anchoring groups

HN

Ar

2H-6

(

2H-16 and 2H-17) for the further design of hybrid materials.

2H-(14-19)

Meanwhile, this methodology is also suitable for the

preparation of porphyrins bearing a receptor unit at the

periphery of the tetrapyrrolic macrocycle (2H-18 and 2H-19).

All compounds were unambiguously characterized by NMR,

ESI-MS, IR and UV-vis spectra and all data were in agreement

with the assigned structures (see ESI).

Br

NO₂

CO₂H

R =

8, 2H-14a (90%)

b (64%)

9, 2H-15a (55%)

10, 2H-16b (65%)

c (56%)

e (50%)

d (69%)

f (51%)

Synthesis of water-soluble conjugates of porphyrins.

N

Finally, these outcomes were used for the preparation of

water-soluble conjugates of porphyrin using peculiar amino

O

N

O

PO(OEt)₂

N

α-sulfo-β-alanine (β

-Ala(SO₃H))^60,61as an effective

O

acid

O

hydrophilic substituent (Scheme 1, 2H-3). Recently, this

sulfonated building block has proven its potential for water

solubilizing of a wide range of organic-based fluorophores and

organic supramolecular compounds through good to high-yield

reactions namely Schotten-Baumann amidification, copper-

catalyzed azide-alkyne 1,3-dipolar cycloaddition (CuAAC, also

named Huisgen–Sharpless-Meldal or "click" reaction) and

palladium-catalyzed Sonogashira reaction.^61-67To apply this

"post-synthetic" sulfonation methodology, an appropriate

porphyrin carboxylic acid should be prepared and converted

into the reactive N-hydroxysuccinimidyl (NHS) ester prior to

12, 2H-18a (49%)

b (48%)

13, 2H-19a (50%)

11, 2H-17b (71%)

Ar = Tol (a), Mes (b), 4-BrC₆H₄(c), 4MeCO₂C₆H₄(d), 4-(EtO)₂P(O)C₆H₄(e),

2,6-Cl₂C₆H₃(f)

Scheme 5. Synthesis of fused porphyrin imidazole systems through Debus-

Radziszewski condensation.

The increase of the aldehyde amount up to 2 equiv did not

influence the product yield (entry 2). In contrast, the reaction

outcome was dependent on the variation of CHCl₃/AcOH ratio.

When 9:1 mixture of CHCl₃/AcOH was used, the product was

aminolysis by

When carboxylic acid 2H-5e was reacted with peptide coupling

uronium reagent O-(N-succinimidyl)-1,1,3,3-

β-Ala(SO₃H) (20).

obtained in 60% yield (entry 3). An over excess of aldehyde

8

tetramethyluronium tetrafluoroborate (TSTU)⁶⁸and DIEA in

dry NMP, only imide 2H-21e was obtained according to the

intramolecular acylation reaction (Scheme 6). In contrast,

appeared to be suited to maximize the formation of the

imidazole under these conditions (entries 4 and 5). Moreover,

it was possible to increase the reaction rate without

deterioration of the product yield replacing AcOH by a

stronger carboxylic acid, TFA (entry 6). However, a large over

carboxylic acids 2H-16b, Zn-16b and Zn-16e bearing the

porphyrin moiety covalently bonded through the imidazole

linker were quantitatively converted into the corresponding

NHS esters 2H-22b and Zn-22b,e (Scheme 6). Thereafter, these

crude NHS esters were reacted with tetrabutylammonium

excess of aldehyde

8 was still needed for the successful

condensation (entries 6-8).

On the basis of these outcomes, the reactions of 2,3-dioxo-

5,10,15,20-tetraarylchlorins 2H-6a-f with an excess of aromatic

(TBA) salt of

α-sulfo-β-alanine (20) under anhydrous

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ARTICLE

O

Ar HN

CO₂H

Ar

N

O

NH

N

i

NH

N

CO₂H

Ar

H₂N

HN

Bu₄N

SO₃

20

HN

Ar

Ar = Mes (b), 4-(EtO)₂P(O)C₆H₄(e)

2H-5e

2H-21e (42%)

O

CO₂H

_

CO₂H

N

O

NH

+

SO₃

Et₃NH

O

Ar

M

Ar

HN

N

i

N

ii

Ar

M

Ar

M

Ar

2H-16b, Zn-16b, Zn-16e

Ar

2H-22b, Zn-22b, Zn-22e

2H-3b, Zn-3b, Zn-3e

Scheme 6. Synthesis of water-soluble porphyrins 2H-3 and Zn-3. Reagents and conditions: i. TSTU, DIEA, NMP, r.t.; ii. 20, DIEA, NMP, 4 °C to r.t.

conditions to give water-soluble porphyrins 2H-3b, Zn-3b and

Zn-3e (Scheme 6). This post-synthetic derivatization was

performed in organic media both to minimize the premature

hydrolysis and to suppress the precipitation of the involved

active NHS ester of porphyrins, frequently encountered using

standard Schotten–Baumann aqueous conditions.^69-71RP-HPLC

purification using aqueous triethylammonium bicarbonate

(TEAB) buffer and acetonitrile as eluents, followed by

Conclusion

Synthetic approaches to functionalized porphyrins and

porphyrin conjugates from meso-tetraarylporphyrins through

the acylation and the oxidation of

β-aminoporphyrins were

investigated. A series of meso-tetraarylporphyrin conjugates

bearing water-soluble moieties, anchoring groups and

receptor subunits was prepared by use of two steps

methodology consisting of their oxidation to 2,3-dioxochlorins

followed by Debus-Radziszewski condensation of these diones

with aromatic aldehydes in the presence of AMAC. The

experimental parameters influencing the outcome of these

reactions were briefly investigated and valuable procedures

tolerating the variation of the substitution pattern of

-aminoporphyrins and aldehydes were developed. The

reported results demonstrate mildness and usefulness of this

lyophilisation provided 2H-3b, Zn-3b and Zn-3e in a pure form

(isolated yields were about 50%).

Free base conjugate 2H-3b and Zn complexes Zn-3b,e were

soluble in water and related aqueous buffers in

a

concentration range (1.0 ꢀM to 1.0 mM) suitable for bio-

labeling applications. The photophysical properties of

fluorophore Zn-3b were evaluated in acetonitrile and under

simulated physiological conditions (PBS, i.e., phosphate

buffered saline, 100 mM phosphate + 150 mM NaCl, pH 7.5).

Being excited at 427 nm, this fluorophore exhibits in

acetonitrile a low red fluorescence emission (602 and 657 nm)

with a 2.5% quantum yield. However, Zn-3b is non-emissive

under physiological conditions that can be explained by the

aggregation of porphyrin in aqueous media. Further

optimization of the structural parameters of this long-

wavelength fluorophore is needed for its use in physiological

medium.

methodology for the preparation of modular

β-substituted

meso-tetraarylporphyrins required in optics, sensing,

biomedicine and material chemistry. In very successful on-

going work in our laboratory, the meso-tetraarylporphyrins

equipped with anchoring groups, 2H-16 and 2H-17, are being

used in the development of hybrid organic-inorganic catalysts

for oxidation reactions. These studies will be reported soon.

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ARTICLE

Moléculaire", the technological platform for chemical analysis

and molecular synthesis (http://www.wpcm.fr) which relies on

the Institute of the Molecular Chemistry of University of

Burgundy and Welience^TM, a Burgundy University private

subsidiary.

Experimental

Materials and instruments

Unless otherwise noted, all chemicals and starting materials

were obtained commercially from Acros® or Aldrich® and used

without further purification. The starting free-base porphyrins,

RP-HPLC purifications were performed on a Thermo-Dionex

5,10,15,20-tetratolylporphyrin

(

2H-1a),⁷²

5,10,15,20-

Ultimate 3000 instrument equipped with

Detector (four distinct wavelengths).

a

RS Variable

Fluorescence

tetramesitylporphyrin

bromophenyl)porphyrin

(

2H-1b),⁷³

2H-1c),⁷⁴

5,10,15,20-tetrakis(4-

(

spectroscopic studies (emission/excitation spectra) were

performed with an HORIBA Jobin Yvon Fluorolog

spectrophotometer (software FluorEssence) with a standard

fluorometer cell (Labbox, LB Q, 10 mm). Emission spectra were

recorded after excitation at the corresponding wavelength

(shutter: Auto Open, excitation slit = 4 nm and emission slit = 4

nm). All fluorescence spectra were corrected.

methylcarboxyphenyl)porphyrin

(

2H-1d),⁷⁵

5,10,15,20-

2H-1e),⁷⁶

2H-1f),⁷⁷

2H-

were prepared according to published procedures.

[5,10,15,20-Tetrakis(pentafluorophenyl)porphyrinato]nickel

Ni-1g) was prepared according to the literature procedure.⁷⁹

tetrakis(4-diethoxyphosphorylphenyl) porphyrin

5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin

(

and 5,10,15,20-tetrakis (pentafluorophenyl)porphyrin

(

78

1g

)

(

Fluorescence quantum yield of Zn-3b was measured at 25 °C

by a relative method using Ru(bpy)₃Cl₂(Φ_F= 4.2% in water) as

a standard.⁸³The following equation was used to determine

the relative fluorescence quantum yield:

4’-(4-Formylphenyl)-2,2’:6’,2’’-terpyridine was prepared from

4’-(4-methylphenyl)-2,2’:6’,2’’-terpyridine⁸⁰according to the

literature procedure.⁸¹4’-Formylbenzo-15-crown-5 was

prepared according to the literature procedure.⁸²Phosphate

buffered saline (PBS, 100 mM phosphate + 150 mM NaCl, pH

7.5) and aqueous mobile-phases for HPLC were prepared using

water purified with a PURELAB Ultra system from ELGA

(purified to 18.2 MΩ cm). Peptide synthesis grade DIEA was

provided by Iris Biotech GmbH. Triethylammonium

bicarbonate (TEAB, 1.0 M) buffer was prepared from distilled

ꢃ ∗ ꢄ^ꢂ∗ ꢅ^ꢆ

ꢀ_ꢁ= ꢀ_ꢁ^ꢂ

ꢃ^ꢂ∗ ꢄ ∗ ꢅ_ꢇ^ꢆ

where A is the absorbance (in the range of 0.01-0.1 a.u.), F is

the area under the emission curve, n is the refractive index of

the solvents (at 25 °C) used in measurements, and the

subscript s represents the standard. The following refractive

index value is used: 1.333 for water and 1.341 for CH₃CN.

Several chromatographic systems were used for the

purification steps: System A: semi-preparative RP-HPLC

(SiliCycle SiliaChrom C₁₈column, 10 μm, 20 × 250 mm) with

CH₃CN and aqueous TEAB (50 mM, pH 7.5) as eluents [0%

CH₃CN (5 min), followed by a gradient of 0% to 20% CH₃CN (10

min), then 20% to 100% CH₃CN (80 min)] at a flow rate of 20.0

mL/min. Quadruple UV-vis detection was achieved at 220, 260,

430 and 450 nm. System B: system A with the following

gradient [20% CH₃CN (5 min), followed by a gradient of 20% to

60% CH₃CN (20 min), then 60% to 100% CH₃CN (40 min)].

Quadruple UV-vis detection was achieved at 220, 260, 423 and

450 nm. System C: system A with the following gradient [10%

CH₃CN (5 min), followed by a gradient of 10% to 100% CH₃CN

(45 min)]. Quadruple UV-vis detection was achieved at 220,

260, 427 and 450 nm.

TEA and CO₂gas.

reported procedures.^60,61

β-Ala(SO₃H) was prepared according to

All reactions were performed in air unless otherwise stated.

The photooxidation was carried out using a Luzchem Ring

Illuminator (Model RING-01, visible light ring, 22 W) or bulb

lamb (200 W). Analytical thin-layer chromatography (TLC) was

carried out using Merck silica gel 60 plates (precoated sheets,

0.2 mm thick, with fluorescence indicator F254). Column

chromatography purification was carried out on silica gel (Silica

60, 63-200 μm, Aldrich) and neutral alumina (Aluminium oxide

90, 63-200 μm, Merck).

NMR spectra were acquired on Bruker Avance III 600 MHz,

Bruker Avance III 500 MHz and Bruker Avance III Nanobay 300

MHz spectrometers and referenced to solvent residual

protons. UV-visible spectra were obtained on a Varian Cary 50

spectrophotometer and THERMO Scientific Evolution 201 by

using a rectangular quartz cell (Hellma, 100-QS, 45

× 12.5 ×

12.5 mm, pathlength 10 mm, chamber volume: 3.5 mL).

MALDI-TOF mass-spectra were obtained on a Bruker Ultraflex

II LRF 2000 mass-spectrometer in positive ion mode unless

otherwise stated with dithranol matrix. Low-resolution MS

analyses were performed on a Bruker Amazon LS (ion trap) in

positive mode unless otherwise stated. Accurate mass

measurements (HRMS) were made on a THERMO LTQ Orbitrap

XL. Solutions in CHCl₃/methanol (1:1) were used for the

analysis. IR spectra were registered on FT-IR Nexus (Nicolet)

and Bruker Vector 22 spectrophotometers. Micro-ATR

accessory (Pike) was used in order to obtain IR spectra of

polycrystalline solid complexes. All the spectrometers except

THERMO Scientific Evolution 201, Nexus (Nicolet) and Bruker

Avance III 600 MHz were available at the "Pôle Chimie

Procedure for the synthesis of copper (II) and nickel (II) 2-

nitrotetraarylporphyrinates (Cu-4a-f and Ni-4g).

Copper (II) and nickel (II) nitrotetraarylporphyrinates, Cu-4a,

Cu-4b, Cu-4c, Cu-4d, Cu-4e, Cu-4f and Ni-4g, were prepared

according to

a modified literature protocol for similar

compounds.¹⁹Experimental conditions for the preparation of

these compounds are summarized in Table S1 (see ESI). The

detailed experimental procedures for the preparation of novel

compounds are given below.

[2-Nitro-5,10,15,20-tetratolylporphyrinato]copper(II) (Cu-4a)

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Journal Name

5,10,15,20-Tetratolylporphyrin (2H-1a) (335 mg, 0.5 mmol) progress of the reaction was monitored by TLC. On the

was dissolved in CHCl₃(500 mL). Glacial acetic acid (5 mL), completion of the nitration reaction, the mixture was cooled

acetic anhydride (31 mL), copper nitrate trihydrate (334 mg, and 100 mL of water were added. Acetic acid was neutralized

1.38 mmol) were added to the solution. The reaction mixture with aqueous sodium carbonate. The organic phase was

was stirred at r.t. for 16 h. The progress of the reaction was washed twice with water (50 mL × 2) and dried over anhydrous

monitored by TLC. On completion of the nitration reaction, the sodium sulfate. The solvent was removed under reduced

mixture was cooled and 200 mL of water were added. Acetic pressure. The resulting crude solid was purified by silica gel

acid was neutralized with aqueous sodium carbonate. The column chromatography using

a CH₂Cl₂/MeOH (99.9:0.1)

organic phase was washed with water twice (200 mL × 2), mixture to afford Cu-4d (151 mg, 79%) as a purple solid.

dried over sodium sulfate anhydrous. The solvent was HRMS (ESI+): m/z calcd for (C₅₂H₃₅CuN₅NaO₁₀)⁺: 975.15721;

removed under reduced pressure. The resulting crude solid found: 975.15468 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 428 (4.93),

was purified by silica gel column chromatography using a 550 (3.80), 592 (3.64). IR: ν_max/cm^-12957 (m), 2925 (m), 2856

hexane/CH₂Cl₂(7:3) mixture to afford Cu-4a (263 mg, 68%) as a (m), 1718 (s, C=O), 1607 (m), 1523 (m, NO₂), 1462 (m), 1434

purple solid.

(m), 1406 (m), 1378 (m, NO₂), 1266 (s), 1248 (s), 1193 (w),

HRMS (ESI): m/z calcd for (C₄₈H₃₅CuN₅O₂)⁺: 776.20813; found: 1174 (w), 1113 (s), 1100 (s), 1018 (m), 998 (m), 960 (w), 924

776.20905 [M]⁺. λ_max(CHCl₃)/nm (log ε) 422 (5.08), 551 (3.86), (w), 874 (m), 846 (w), 821 (m), 804 (m), 794 (m), 764 (m), 729

593 (3.70). IR: ν_max/cm^-12956 (m), 2922 (m), 2853 (m), 1722 (s), 707 (m).

(s), 1527 (m, NO₂), 1505 (m), 1456 (m), 1377 (m, NO₂), 1339

[2-Nitro-5,10,15,20-tetrakis(4-diethoxyphosphorylphenyl)porphy-

(m), 1329 (m), 1305 (w), 1266 (s), 1247 (s), 1180 (m), 1114 (s),

rinato]copper(II) (Cu-4e)

1101 (s), 1074 (m), 1019 (m), 998 (s), 967 (m), 923 (m), 873

5,10,15,20-Tetrakis(4-diethoxyphosphorylphenyl)porphyrin

(w), 845 (m), 822 (m), 796 (s), 751 (m), 729 (s), 688 (m).

(

2H-1e) (301 mg, 0.26 mmol) was dissolved in acetic anhydride

[2-Nitro-5,10,15,20-tetramesitylporphyrinato]copper(II) (Cu-4b)

(70 mL) and copper nitrate trihydrate (252 mg, 1.04 mmol) was

The compound Cu-4b was obtained from 2H-1b in 90% (400 added to the solution. The reaction mixture was heated up to

mg) yield as a purple solid. Spectral data are in agreement with 120 °C and kept at this temperature for 5-10 min. The progress

those reported in the literature.⁸⁴

of the reaction was controlled by MALDI spectrometry because

the starting compound and the product have the same R_f

which restricts TLC control. On the completion of the nitration

reaction, the acetic anhydride was distilled from the reaction

mixture under reduced pressure. The residue was dissolved in

CH₂Cl₂and the solution was washed twice with water (100 mL

× 2). The organic phase was dried over anhydrous sodium

sulfate. The solvent was removed under reduced pressure. The

resulting crude solid was purified by silica gel column

chromatography using a CH₂Cl₂/MeOH (97:3) mixture to afford

Cu-4e (270 mg, 82%) as a purple solid.

HRMS (ESI+): m/z calcd for (C₆₀H₆₃Br₄CuN₅NaO₁₄)⁺:

1287.25102; found: 1287.25576 [M+Na]⁺. λ_max(CHCl₃)/nm (log

ε) 426 (5.26), 549 (4.09), 592 (3.97). IR: ν_max/cm^-13430 (w),

2982 (w), 2906 (w), 1601 (m), 1520 (m, NO₂), 1442 (w), 1390

(m), 1337 (m, NO₂), 1239 (s, P=O), 1161 (m, P-O), 1129 (m),

1098 (w), 1047 (m), 1012 (s), 955 (s, P-O), 794 (s), 764 (s), 717

(s), 584 (s).

[2-Nitro-5,10,15,20-tetrakis(4-bromophenyl)porphyrinato]copper

(II) (Cu-4c)

5,10,15,20-Tetrakis(4-bromophenyl)porphyrin

(

2H-1c

)

(437

mg, 0.47 mmol) was dissolved in CHCl₃(305 mL). Glacial acetic

acid (7 mL), acetic anhydride (42 mL), copper (II) nitrate

trihydrate (796 mg, 3.29 mmol) were added to the solution.

The reaction mixture was refluxed for 2 h. The progress of

reaction was monitored by TLC. On the completion of

nitration, the reaction mixture was cooled and 200 mL of

water were added. Acetic acid was neutralized with aqueous

solution of sodium carbonate. The organic phase was washed

twice with water (200 mL × 2) and dried over anhydrous

sodium sulfate. The solvent was removed under reduced

pressure. The resulting crude solid was purified by silica gel

column chromatography using a hexane/CH₂Cl₂(3:2) mixture

to afford Cu-4c (341 mg, 70%) as a purple solid.

HRMS (ESI+): m/z calcd for (C₄₄H₂₃Br₄CuN₅NaO₂)⁺: 1054.77735;

found: 1054.77896 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 425 (5.14), [2-Nitro-5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrinato]-

549 (4.00), 590 (3.81). IR: ν_max/cm^-12956 (m), 2923 (m), 2855 copper (II) (Cu-4f)

(m), 1720 (s), 1586 (m), 1522 (s, NO₂), 1482 (s), 1374 (m, NO₂), 5,10,15,20-Tetrakis(2,6-dichlorophenyl)porphyrin (2H-1f) (890

1338 (s), 1267 (s), 1196 (w), 1162 (w), 1114 (m), 1100 (m), mg, 1.0 mmol) was dissolved in CHCl₃(695 mL). Glacial acetic

1070 (s), 997 (s), 922 (m), 849 (m), 825 (m), 795 (s), 752 (s), acid (15 mL), succinic anhydride (5 g, 50.0 mmol) and copper

726 (s), 698 (m).

nitrate trihydrate (1.21 g, 5.0 mmol) were added to the

solution. The reaction mixture was refluxed for 30 min. The

reaction progress was monitored by TLC. The reaction mixture

was cooled after completion of nitration and 200 mL of water

were added. Acetic acid was neutralized with aqueous solution

of sodium carbonate. The organic phase was washed twice

with water (200 mL × 2) and dried over anhydrous sodium

sulfate. The solvent was removed under reduced pressure. The

[2-Nitro-5,10,15,20-tetrakis(4-

methylcarboxyphenyl)porphyrinato]copper(II) (Cu-4d)

5,10,15,20-Tetrakis(4-methylcarboxyphenyl)porphyrin (2H-1d

)

(169 mg, 0.2 mmol) was dissolved in CHCl₃(130 mL). Glacial

acetic acid (3 mL), succinic anhydride (1 g, 10 mmol), copper

nitrate trihydrate (242 mg, 1.0 mmol) were added to the

solution. The reaction mixture was stirred at r.t. for 10 h. The

8 | New J. Chem., 2016, 00, 1-3

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ARTICLE

resulting crude solid was purified by silica gel column completion of demetallation (10-30 min), the reaction mixture

chromatography using a hexane/CH₂Cl₂(1:1) mixture to afford was washed twice with water (50 mL × 2), saturated solution

Cu-4f (748 mg, 75%) as a purple solid. Spectral data are in of sodium carbonate (30 mL) and with water (50 mL) to

agreement with those reported in the literature.²⁷

neutralize sulfuric acid. The organic phase was separated and

dried over anhydrous sodium sulfate. The solvent was

evaporated under reduced pressure. The resulting crude solid

was purified by silica gel column chromatography to afford the

[5,10,15,20-Tetrakis(pentafluorophenyl)porphyrinato]copper (II)

(Cu-1g)

5,10,15,20-Tetrakis(pentafluorophenyl)porphyrin (2H-1g) (98

mg, 0.1 mmol) was dissolved in CHCl₃(65 mL). Glacial acetic

appropriate 2-nitro-5,10,15,20-tetraarylporphyrin 2H-4

.

acid (1.5 mL), succinic anhydride (500 mg, 5.0 mmol) and 2-Nitro-5,10,15,20-tetratolylporphyrin (2H-4a) was obtained

copper nitrate trihydrate (121 mg, 0.5 mmol) were added to in 74% (159 mg) yield as a purple solid. It has already been

the solution. The reaction mixture was refluxed for the night, described. Spectral data are in agreement with those reported

washed with water (30 mL × 2) and dried over anhydrous in the literature.⁸⁷

sodium sulfate. The solvent was removed under reduced

2-Nitro-5,10,15,20-tetramesitylporphyrin

(2H-4b)

was

pressure. The resulting crude solid was purified by short silica

gel column using a hexane/CH₂Cl₂(1:1) mixture to afford Cu-1g

with quantitative yield (107 mg).

prepared according to the literature protocol⁸⁴and was

obtained in 80% (198 mg) yield as a purple solid. Spectral data

are in agreement with those reported in the literature.⁸⁴

Spectral data are in agreement with those reported in the

literature.⁸⁵

2-Nitro-5,10,15,20-tetrakis(4-bromophenyl)porphyrin (2H-4c)

was obtained in 88% (257 mg) yield as a purple solid. δ_H(600

MHz; CDCl₃; 25 °C) -2.72 (2 H, br s, internal NH), 7.84 (2 H, d, J

= 8.3 Hz, Br-Ph_meta), 7.91 (4 H, d, J = 8.3 Hz, Br-Ph_meta), 7.92 (2

H, d, J = 8.3 Hz, Br-Ph_meta), 8.02 (2 H, 2d, J = 8.3 Hz, Br-Ph_ortho),

8.03 (2 H, 2d, J = 8.3 Hz, Br-Ph_ortho), 8.05 (2 H, d, J = 8.3 Hz, Br-

Ph_ortho), 8.06 (2 H, d, J = 8.3 Hz, Br-Ph_ortho), 8.68 and 8.70 (2 H,

AB system, J_AB= 4.7 Hz, 12,13-H_β), 8.87 (1 H, d, J = 4.9 Hz, 17-

H_β), 8.88 and 8.92 (2 H, AB system, J_AB= 4.9 Hz, 7,8-H_β), 8.95 (1

H, d, J = 4.9 Hz, 18-H_β), 9.01 (1 H, s, 3-H_β) ppm. HRMS (ESI+):

m/z calcd for (C₄₄H₂₆Br₄N₅O₂)⁺: 971.88145; found: 971.88277

[M+H]⁺. λ_max(CHCl₃)/nm (log ε) 430 (5.22), 528 (4.08), 562,

(3.56), 604 (3.50), 666 (3.84). IR: ν_max/cm^-13325 (w, NH), 2956

(m), 2923 (m), 2854 (m), 1721 (s), 1526 (m, NO₂), 1471 (m),

1344 (m, NO₂), 1266 (s), 1246 (s), 1177 (w), 1158 (m), 1116 (s),

1100 (s), 1070 (s), 1011 (s), 994 (m), 981 (m), 963 (m), 914 (m),

874 (m), 845 (m), 822 (m), 796 (s), 750 (m), 729 (s), 695 (m).

[2-Nitro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrinato]-

nickel(II) (Ni-4g)

The porphyrin Ni-1g (670 mg, 0.65 mmol) was dissolved in

CHCl₃(115 mL). Glacial acetic acid (6 mL), succinic anhydride

(3.25 g, 32.5 mmol) and copper nitrate trihydrate (787 mg,

3.25 mmol) were added to the solution. The reaction mixture

was refluxed for 24 h. The progress of the reaction was

monitored by TLC. On the completion of the nitration reaction,

the mixture was cooled and 100 mL of water were added.

Acetic acid was neutralized with aqueous solution of sodium

carbonate. The organic phase was washed with water (100 mL

× 2) and dried over anhydrous sodium sulfate. The solvent was

removed under reduced pressure. The resulting crude solid

was purified by silica gel column chromatography using a

hexane/CH₂Cl₂(4:1) mixture to afford Ni-4g (615 mg, 88%) as a

purple solid.

δ_H(600 MHz; CDCl₃; 25 °C) 8.66 (1 H_A, AB system, J = 5.1 Hz, 17-

H_β), 8.67–8.73 (4 H, m, 7,8,12,13-H_β), 8.74 (1 H_B, AB system, J =

5.1 Hz, 18-H_β), 9.05 (1 H, 3-H_β) ppm. δ_F(282 MHz; CDCl₃; 25 °C)

-161.32 – -161.08 (2 F, m), -160.73 – -160.49 (4 F, m), -160.30 –

-160.08 (2 F, m), -150.39 (2 F, t, J = 21.3 Hz), -149.96 (1 F, t, J =

21.3 Hz), -149.76 (1 F, t, J = 21.3 Hz), -137.55 – -137.38 (2 F, m),

-136.66 – -136.49 (4 F, m), -136.45 – -136.29 (2 F, m) ppm.

HRMS (ESI+): m/z calcd for (C₄₄H₇F₂₀N₅NaNiO₂)⁺: 1097.95261;

found: 1097.95551 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 419 (4.92),

536 (3.77), 584 (3.83). IR: ν_max/cm^-12930 (w), 2859 (w), 1557

(m), 1519 (s), 1516 (s, NO₂), 1489 (s), 1428 (s), 1337 (s, NO₂),

1300 (m), 1213 (m), 1192 (m), 1154 (m), 1083 (m), 1060 (s),

1012 (m), 983 (s), 964 (m), 954 (s), 943 (s), 925 (s), 878 (m),

817 (s), 802 (s), 773 (s), 760 (s), 714 (s), 706 (s), 667 (m).

2-Nitro-5,10,15,20-tetrakis(4-methylcarboxyphenyl)porphyrin

(2H-4d) was obtained in 95% (254 mg) yield as a purple solid.

δ_H(600 MHz; CDCl₃; 25 °C) -2.67 (2 H, br s, internal NH), 4.06 (3

H, s, CH₃), 4.10 (6 H, s, CH₃), 4.11 (3 H, s, CH₃), 8.25 (2 H, d, J =

8.0 Hz, MeCO₂-Ph_ortho), 8.26 (2 H, d, J = 8.0 Hz, MeCO₂-Ph_ortho),

8.28 (2 H, d, J = 8.0 Hz, MeCO₂-Ph_ortho), 8.30 (2 H, d, J = 8.0 Hz,

MeCO₂-Ph_ortho), 8.38 (2 H, d, J = 8.0 Hz, MeCO₂-Ph_meta), 8.44 (4

H, d, J = 8.0 Hz, MeCO₂-Ph_meta), 8.45 (2 H, d, J = 8.0 Hz, MeCO₂-

Ph_meta), 8.66 and 8.67 (2 H, AB system, J_AB= 4.8 Hz, 12,13-H_β),

8.85 (1 H, d, J = 5.0 Hz, 17-H_β), 8.87 and 8.90 (2 H, AB system,

J_AB= 4.9 Hz, 7,8-H_β), 8.96 (1 H, d, J = 5.0 Hz, 18-H_β), 9.00 (1 H, s,

3-H_β) ppm. HRMS (ESI+): m/z calcd for (C₅₂H₃₇N₅NaO₁₀)⁺:

914.24326; found: 914.23963 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε)

429 (4.94), 527 (3.75), 603 (3.20), 666 (3.52). IR: ν_max/cm^-1

2957 (m), 2927 (m), 2858 (m), 1719 (s, C=O), 1606 (m), 1463

(m, NO₂), 1433 (m), 1406 (m), 1380 (m, NO₂), 1266 (s), 1248

(s), 1189 (m), 1174 (w), 1113 (s), 1100 (s), 1019 (m), 961 (m),

873 (m), 819 (w), 797 (m), 762 (m), 729 (s), 707 (m).

General procedure for the preparation of the free-base 2-nitro-

5,10,15,20-tetraarylporphyrins 2H-4a, 2H-4c-e.⁸⁶

[2-Nitro-5,10,15,20-tetraarylporphyrinato]copper(II) Cu-4 (0.3

mmol) was dissolved in CH₂Cl₂(110 mL). Concentrated H₂SO₄

(1.3 mL) was added dropwise to the vigorously stirred solution.

The progress of reaction was monitored by TLC. On the

2-Nitro-5,10,15,20-tetrakis(4-diethoxyphosphorylphenyl)por-

phyrin (2H-4e) was obtained in 88% (318 mg) yield as a purple

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solid. δ_H(500 MHz; CDCl₃; 25 °C) -2.69 (2 H, br s, internal NH), of sodium carbonate (5%) was added to neutralize the reaction

1.47 (6 H, t, J = 7.2 Hz, CH₃), 1.50 (12 H, t, J = 7.2 Hz, CH₃), 1.51 mixture. The organic phase was separated, washed twice with

(6 H, t, J = 7.2 Hz, CH₃), 4.26–4.43 (16 H, m, CH₂), 8.14 (2 H, dd, water (50 mL × 2) and dried over anhydrous sodium sulfate.

J_PH= 13.2 Hz, J = 8.1 Hz, (EtO)₂OP-Ph_meta), 8.19–8.25 (6 H, m, Solvent was removed under reduced pressure. 2H-2e and 2H-

(EtO)₂OP-Ph_meta), 8.28 (2 H, dd, J = 8.1 Hz, J_PH= 4.0 Hz, 2g were isolated by column chromatography using degassed

(EtO)₂OP-Ph_ortho), 8.29 (2 H, dd, J = 8.1 Hz, J_PH= 4.0 Hz, eluents. Other compounds were oxidized without additional

(EtO)₂OP-Ph_ortho), 8.30 (2 H, dd, J = 8.1 Hz, J_PH= 4.0 Hz, purification.

(EtO)₂OP-Ph_ortho), 8.32 (2 H, dd, J = 8.1 Hz, J_PH= 4.0 Hz,

2-Amino-5,10,15,20-tetrakis(4-diethoxyphosphorylphenyl)-

(EtO)₂OP-Ph_ortho), 8.66 and 8.67 (2 H, AB system, J = 5.0 Hz,

porphyrin (2H-2e) was obtained from 2H-4e (27 mg, 0.023

12,13-H_β), 8.86 (1 H, d, J = 5.0 Hz, 17-H_β), 8.87 and 8.89 (2 H,

AB system, J = 5.0 Hz, 7,8-H_β), 8.97 (1 H, s, 3-H_β), 8.98 (1 H, d, J

= 5.0 Hz, 18-H_β) ppm. δ_P(202 MHz; CDCl₃; 25 °C) 18.03 (1 P),

18.29 (1 P), 18.36 (2 P) ppm. HRMS (ESI+): m/z calcd for

(C₆₀H₆₆N₅O₁₄P₄)⁺: 1204.35512; found: 1204.35785 [M+H]⁺, m/z

calcd for (C₆₀H₆₅N₅NaO₁₄P₄)⁺: 1226.33707; found: 1226.33805

[M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 426 (5.34), 526 (4.14), 599

(3.65), 664 (3.79). IR: ν_max/cm^-13430 (w), 2981 (m), 2915 (m),

2849 (m), 1735 (m), 1601 (m), 1561 (w), 1439 (w), 1390 (m),

1233 (S), 1161 (m), 1129 (m), 1094 (w), 1046 (m), 1010 (s), 962

(s), 793 (s), 759 (s), 717 (s), 698 (s), 578 (s), 543 (s).

mmol) in 56% (15 mg) yield as a purple solid after purification

by column chromatography on alumina using degassed CHCl₃.

δ_H(300 MHz; CDCl₃; 25 °C) -2.85 (2 H, very br s, internal NH),

1.49 (24 H, t, J = 7.1 Hz, CH₃), 4.29–4.44 (16 H, m, CH₂), 7.68 (1

H, s, 3-H_β), 8.12–8.31 (16 H, m, (EtO)₂OP-Ph), 8.41 (1 H, d, J =

4.9 Hz, 18-H_β), 8.63 (1 H, d, J = 4.9 Hz, 7-H_β), 8.66 (1 H, d, J =

4.9 Hz, 17-H_β), 8.72 (1 H, d, J = 4.9 Hz, 8-H_β), 8.74 (2 H, AB

system, 12,13-H_β) ppm, NH₂protons are not observed. δ_P(121

MHz; CDCl₃; 25 °C) 17.88 (1 P), 18.87 (1 P), 18.92 (1 P), 18.98 (1

P) ppm. HRMS (ESI+): m/z calcd for (C₆₀H₆₈N₅O₁₂P₄)⁺:

1174.38094; found: 1174.38164 [M+H]⁺. λ_max(CHCl₃)/nm (log ε)

2-Nitro-5,10,15,20-tetrakis(2,6-dichlorophenyl)porphyrin (2H- 403 (5.26), 524 (3.98), 593 (3.64), 652 (3.62) 672 (3.13). IR:

4f) was prepared according to the literature protocol.²⁷This ν_max/cm^-13460 (w, NH), 3312 (w, NH), 2979 (m), 2905 (m),

compound was obtained from Cu

-4f (200 mg, 0.2 mmol) in 1632 (w), 1599 (m), 1538 (m), 1453 (m), 1390 (m), 1238 (s,

75% (141 mg) yield as a purple solid.

P=O), 1162 (m), 1128 (s, P-O), 1095 (w), 1047 (m), 1013 (s, P-

δ_H(600 MHz; CDCl₃; 25 °C) -2.48 (2 H, br s, internal NH), 7.67 (1 O), 956 (s), 788 (s), 765 (s),717 (s), 579 (s).

H, t, J = 8.5 Hz, Cl₂Ph_para), 7.70 (2 H, t, J = 8.5 Hz, Cl₂Ph_para),

2-Amino-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin

7.705 (2 H, d, J = 8.5 Hz, Cl₂Ph_meta), 7.71 (1 H, t, J = 8.5 Hz,

Cl₂Ph_para), 7.78 (6 H, d, J = 8.5 Hz, Cl₂Ph_meta), 8.53 and 8.54 (2 H,

AB system, J_AB= 4.6 Hz, 12,13-H_β), 8.70 (1 H_A, AB system, J =

4.9 Hz, 17-H_β), 8.72 (2 H, 2d, J = 4.9 Hz, 7,8-H), 8.74 (1 H_B, AB

system, J = 4.9 Hz, 18-H_β), 8.90 (1 H, s, 3-H_β) ppm. HRMS (ESI+):

m/z calcd for (C₄₄H₂₂Cl₈N₅O₂)⁺: 931.92762; found: 931.93118

[M+H]⁺. λ_max(CHCl₃)/nm 424 (5.42), 523 (4.22), 558 (3.72), 601

(4.03), 656 (3.49). IR: ν_max/cm^-13337 (w, NH), 2922 (m), 2852

(m), 1723 (m), 1557 (m), 1520 (m, NO₂), 1427 (s), 1359 (m,

NO₂), 1337 (m), 1268 (m), 1220 (w), 1191 (m), 1152 (m),

1102(m), 1018 (w), 994 (m), 981 (m), 963 (m), 919 (w), 881

(m), 846 (m), 829 (m), 802 (s), 784 (s), 774 (s), 714 (s), 641 (m).

(2H-2g) was obtained from 2H-4g (39 mg, 0.038 mmol) in (20

mg, 53%) yield as a purple solid after purification by silica gel

column chromatography using degassed hexane/CH₂Cl₂(7:3)

mixture.

δ_H(300 MHz; CDCl₃; 25 °C) -2.78 (2 H, very br s, internal NH),

4.65 (2 H, br s, NH₂), 7.82 (1 H, s, 3-H_β), 8.61 (1 H, d, J = 4.8 Hz,

18-H_β), 8.74 (1 H, d, J = 4.8 Hz, 7-H_β), 8.77–8.83 (2 H, m, 8,17-

H_β), 8.81 and 8.85 (2 H, AB system, J_AB= 4.8 Hz, 12,13-H_β) ppm.

δ_F(282 MHz; CDCl₃; 25 °C) -161.83 − -161.43 (6 F, m), -159.81 −

-159.56 (2 F, m), -152.11 (1 F, t, J = 20.8 Hz), -151.64 (1 F, t, J =

20.8 Hz), -151.60 (1 F, t, J = 20.8 Hz), -149.92 (1 F, t, J = 20.8

Hz), -136.74 – -136.50 (6 F, m), -135.64 – -135.46 (2 F, m).

2-Nitro-5,10,15,20-tetrakis(pentafluorophenyl)porphyrin (2H- HRMS (ESI+): m/z calcd for (C₄₄H₁F₂₀N₅Na)⁺: 1012.05873;

4g) was prepared by using the literature protocol for found: 1012.05694 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 401 (5.08),

corresponding copper(II) complexes.²⁷The free-base porphyrin 517 (4.06), 590 (3.68), 645 (3.61), 673 (3.54). IR: ν_max/cm^-1

2H-4g was obtained from Ni-4g (75 mg, 0.07 mmol) in 56% (40 3475 (w, NH), 3391 (w, NH), 3311 (w), 2923 (m), 2853 (m),

mg) yield as a purple solid. Spectral data are in agreement with 1729 (m), 1648 (m), 1612 (m), 1515 (s), 1496 (s), 1346 (m),

those reported in the literature.²⁷

1319 (m), 1261 (w), 1215 (w), 1143 (m), 1082 (m), 1025 (m),

987 (s), 919 (s), 850 (w), 804 (m), 756 (s), 723 (m), 705 (m).

General procedure for the preparation of free-base 2-amino-

5,10,15,20-tetraarylporphyrins 2H-2a-g.⁵⁷

Procedure for the preparation of 2-(COOH(CH₂)₂CONH)-5,10,15,20-

tetrakis(4-diethoxyphosphorylphenyl)porphyrin (2H-5e).⁸⁸

Tin(II) chloride dihydrate SnCl₂∙2H₂O (340 mg, 1.5 mmol) and

concentrated hydrochloric acid (3.2 mL) were added to a Succinic anhydride (185 mg, 1.85 mmol) was added to a

solution of 2H-4 (0.15 mmol) in dichloromethane (26 mL) solution of 2H-2e (43 mg, 0.037 mmol) in CH₂Cl₂(15 mL) under

under N₂atmosphere in a light shielded flask. The reaction N₂atmosphere. The reaction mixture was stirred at reflux until

mixture was stirred for 24 h. The reaction was monitored by complete conversion of the amine according to TLC (24 h).

MALDI spectrometry and stopped when the starting Then the reaction mixture was evaporated under reduced

compound was consumed (24-48 h). The reaction mixture was pressure. The residue was chromatographed on a silica gel

diluted with 20 mL of dichloromethane and aqueous solution eluting with a CH₂Cl₂/MeOH (9:1) mixture to afford 2H-5e (35

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mg, 74%) as a purple solid and 2H-6e (7 mg, 16%) as a brown 2.58 (6 H, s, CH_3para), 7.21 (4 H, br s, Mes), 7.23 (4 H, br s, Mes),

4

8.36 (2 H, s, 12,13-H_β), 8.44 (2 H, dd, J = 4.9 Hz, J = 1.7 Hz,

solid.

4

2H-5e δ_H(300 MHz; CDCl₃; 25 °C) -2.89 (2 H, br s, internal NH), 8,17-H_β), 8.54 (2 H, dd, J = 4.9 Hz, J = 1.7 Hz, 7,18-H_β) ppm.

1.49 (24 H, t, J = 6.9 Hz, CH₃), 2.27–2.34 (2 H, m, CH₂), 2.65– HRMS (ESI+): m/z calcd for (C₅₆H₅₂N₄NaO₂)⁺: 835.39825; found:

2.73 (2 H, m, CH₂), 4.27–4.45 (16 H, m, (O-CH₂), 7.62 (1 H, s, 835.40188 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 406 (5.21), 479

NH), 8.10-8.37 (16 H, m, (EtO)₂OP-Ph), 8.57 (1 H, d, J = 4.9 Hz, (4.17), very broad band stretching from 575 nm to 800 nm

H_β), 8.70 (1 H, d, J = 4.9 Hz, H_β), 8.73(2 H, s, H_β), 8.75-8.82 (2 H, centered at about 670 nm. IR: ν_max/cm^-13354 (w, NH), 2913

2 d, J = 5.0 Hz, H_β), 9.21 (1 H, s, 3-H_β) ppm. δ_P(121 MHz; CDCl₃; (m), 2852 (m), 1724 (s, C=O), 1615 (m), 1535 (m), 1455 (m),

25 °C) 17.48 (1 P), 18.65 (2 P), 18.67 (1 P) ppm. HRMS (ESI+): 1407 (w), 1373 (w), 1339 (m), 1287 (w), 1267 (m), 1249 (w),

m/z calcd for (C₆₄H₇₂N₅O₁₅P₄)⁺: 1274.39699; found: 1274.39907 1215 (m), 1187 (s), 1060 (m), 1035 (m), 1019 (m), 993 (m), 981

[M+H]⁺; m/z calcd for (C₆₄H₇₁N₅NaO₁₅P₄)⁺: 1296.37893; found: (m), 969 (m), 947 (m), 850 (m), 828 (m), 803 (s), 756 (s), 719

1296.37956 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 423 (5.43), 519 (s), 689 (s), 667 (m).

(4.32), 550 (3.86), 593 (3.83), 648 (3.40). IR: ν_max/cm^-13422 (w,

2,3-Dioxo-5,10,15,20-tetrakis(4-bromophenyl)chlorin (2H-6c)

NH), 3323 (w, NH), 2979 (m), 2929 (m), 2905 (m), 1723 (s,

was obtained as a brown solid in 64% (160 mg) yield from the

C=O), 1704 (s, amide I), 1599 (s, amide II), 1509 (s), 1475 (m),

crude 2H-2c prepared from 2H-4c (254 mg, 0.29 mmol).

1442 (m), 1389 (s), 1367 (m), 1235 (s, P=O), 1161 (s, P–O),

1127 (s), 1097 (m), 1047 (s), 1012 (s), 955 (s, P–O), 789 (s), 764

(s), 718 (s), 579 (s).

δ_H(300 MHz; CDCl₃; 25 °C) -2.14 (2 H, br s, internal NH), 7.74

and 7.82 (8 H, AB system, J = 8.4 Hz, Br-Ph), 7.88 and 7.97 (8 H,

AB system, J = 8.4 Hz, Br-Ph), 8.54 (2 H, s, 12,13-H_β), 8.60 (2 H,

dd, J = 5.1 Hz, ⁴J = 1.4 Hz, 8,17-H_β), 8.74 (2 H, dd, J = 5.1 Hz, ⁴J =

1.4 Hz, 7,18-H_β) ppm. HRMS (ESI+): m/z calcd for

(C₄₄H₂₅B_r4N₄O₂)⁺: 956.87055; found: 956.87435 [M+H]⁺.

λ_max(CHCl₃)/nm (log ε) 406 (5.09), 471 (4.12), 566 (3.58), 602

(3.55), 655 (3.61). IR: ν_max/cm^-13354 (w, NH), 2956 (m), 2924

(m), 2857 (m), 1721 (s, C=O), 1585 (w), 1486 (m), 1464 (m),

1408 (w), 1392 (m), 1346 (m), 1266 (s), 1248 (s), 1116 (m),

1100 (s), 1071 (m), 1044 (m), 1013 (s), 995 (m), 978 (m), 964

(m), 875 (m), 838 (m), 799 (s), 729 (s), 713 (m), 692 (m), 685

(m), 676( m).

General procedure for the preparation of 2,3-dioxo-5,10,15,20-

tetraarylchlorins 2H-6a-d,f.⁴⁵

To the crude 2-aminotetraarylporphyrin 2H-2 silica gel (525

mg) and CH₂Cl₂(75 mL) were added. The reaction mixture was

stirred under irradiation (lamp bulb or Luzchem Ring

Illuminator) in the open flask for 2 h. The progress of reaction

was monitored by TLC. On the completion of oxidation an

additional portion (1.5 g) of silica gel was added and the

reaction mixture was evaporated under reduced pressure. The

residue was loaded on a top of a silica gel column. The product

was eluted with hexane/CH₂Cl₂(3:2) (2H-6a, 2H-6b, 2H-6c, 2H-

6f) or CH₂Cl₂/methanol (99.8:0.2) mixtures (2H-6d). The yield

2,3-Dioxo-5,10,15,20-tetrakis(4-methylcarboxyphenyl)-

chlorin (2H-6d) was obtained as a brown solid in 70% (61 mg)

of 2H

-6 was calculated using to the amount of 2H-4 introduced

yield from the crude 2H-2d prepared from 2H-4d (89 mg, 0.1

in the reduction (total yield for two steps).

mmol).

δ_H(300 MHz; CDCl₃; 25 °C) -2.11 (2 H, br s, internal NH), 4.06 (6

H, s, CH₃), 4.08 (6 H, s, CH₃), 7.96 (4 H, d, J = 8.4 Hz, MeCO₂-

Ph_meta), 8.18 (4 H, d, J = 8.4 Hz, MeCO₂-Ph_meta), 8.37 (4 H, d, J =

8.4 Hz, MeCO₂-Ph_ortho), 8.41 (4 H, d, J = 8.4 Hz, MeCO₂-Ph_ortho),

2,3-Dioxo-5,10,15,20-tetratolylchlorin (2H-6a) was obtained

as a brown solid in 60% (64 mg) yield from the crude 2H 2a

prepared from 2H 4a (109 mg, 0.15 mmol).

-

δ_H(300 MHz; CDCl₃; 25 °C) -2.01 (2 H, br s, internal NH), 2.65 (6

H, s, CH₃), 2.67 (6 H, s, CH₃), 7.48 (4 H, d, J = 8.0 Hz, Tol_meta),

7.52 (4 H, d, J = 8.0 Hz, Tol_meta), 7.76 (4 H, d, J = 8.0 Hz, Tol_ortho),

7.99 (4 H, d, J = 8.0 Hz, Tol_ortho), 8.56 (2 H, s, 12,13-H), 8.60 (2

H, dd, J = 5.0 Hz, ⁴J = 1.3 Hz, 8,17-H_β), 8.74 (2 H, dd, J = 5.0 Hz,

⁴J = 1.3 Hz, 7,18-H_β) ppm. HRMS (ESI+): m/z calcd for

(C₄₈H₃₇N₄O₂)⁺: 701.29110; found: 701.29076 [M+H]⁺.

λ_max(CHCl₃)/nm (log ε) 407 (5.11), 477 (4.17), very broad band

stretching from 575 nm to 800 nm centered at about 670 nm.

IR: ν_max/cm^-13361 (w, NH), 2956 (m), 2921 (m), 2854 (m), 1725

(vs, C=O), 1505 (m), 1456 (m), 1407 (w), 1378 (m), 1346 (m),

1266 (s), 1248 (m), 1222 (m), 1181 (m), 1109 (m), 1101 (m),

1089 (s), 1065 (m), 1042 (m), 1020 (m), 994 (m), 980 (m), 966

(m), 836 (m), 821 (w), 793(s), 724 (s), 688 (s).

4

8.51 (2 H, s, 12,13-H_β), 8.56 (2 H, dd, J = 5.0 Hz, J = 1.4 Hz,

4

8,17-H_β), 8.71 (2 H, dd, J = 5.0 Hz, J = 1.4 Hz, 7,18-H_β) ppm.

HRMS (ESI+): m/z calcd for (C₅₂H₃₆N₄NaO₁₀)⁺: 899.23236;

found: 899.23386 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 406 (5.26),

471 (4.28). IR: ν_max/cm^-13351 (w, NH), 2953 (m), 2926 (m),

2856 (m), 1716 (s, CO), 1607 (m), 1566 (w), 1454 (m), 1432

(m), 1404 (m), 1383 (w), 1349 (w), 1267 (s), 1191 (m), 1176

(m), 1100 (s), 1067 (m), 1043 (m), 1020 (m), 996 (w), 978 (m),

963 (m), 864 (m), 821 (m), 798 (m), 759 (m), 713 (s), 678 (m),

631 (m).

2,3-Dioxo-5,10,15,20-tetrakis(2,6-dichlorophenyl)chlorin (2H-

6f) was obtained as a brown solid in 66% (90 mg) yield from

the crude 2H-2f prepared from 2H-4f (139 mg, 0.15 mmol).

δ_H(600 MHz; CDCl₃; 25 °C) -1.94 (2 H, br s, internal NH), 7.66 (2 H, t,

J = 8.3 Hz, Cl₂Ph_para), 7.69 (2 H, t, J = 8.3 Hz, Cl₂Ph_para), 7.73 (4 H, d, J

= 8.3 Hz, Cl₂Ph_meta), 7.77 (4 H, d, J = 8.3 Hz, Cl₂Ph_meta), 8.42 (2 H, s,

2,3-Dioxo-5,10,15,20-tetramesitylchlorin

obtained as a brown solid in 80% (300 mg) yield from the

crude 2H 2b prepared from 2H 4b (380 mg, 0.46 mmol).

(2H-6b)

was

-

4

12,13-H_β), 8.55 (2 H, dd, J = 4.8 Hz, J = 1.5 Hz, 8,17-H_β), 8.64 (2 H,

δ_H(300 MHz; CDCl₃; 25 °C) -1.79 (2 H, br s, internal NH), 1.77

dd, J = 4.8 Hz, ⁴J = 1.5 Hz, 7,18-H_β) ppm. HRMS (ESI+): m/z calcd for

(12 H, s, CH_3ortho), 1.85 (12 H, s, CH_3ortho), 2.57 (6 H, s, CH_3para),

(C₄₄H₂₁Cl₈N₄O₂)⁺: 916.91672; found: 916.91873 [M+H]⁺.

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λ_max(CHCl₃)/nm (log ε) 404 (5.27), 469 (4.26), very broad band

stretching from 630 nm to 800 nm centered at about 695 nm.

IR: ν_max/cm-1 3356 (w, NH), 2922 (w), 2849 (w), 1729 (s, C=O),

1557 (m), 1528 (m), 1427 (s), 1343 (m), 1293 (m), 1220 (m),

1191 (m), 1152 (m), 1090 (m), 1063 (m), 1038 (m), 995 (m),

966 (s), 881 (m), 834 (w), 800 (s), 774 (s), 708 (s), 674 (s), 648

(m).

product was eluted with a CHCl₃/MeOH (50:1) mixture as a

rose-violet solid. Yield 33% (5 mg).

δ_H(500 MHz; CDCl₃; 25 °C) 1.24 (6 H, t, J = 7.1 Hz, CH₃), 1.25 (6

H, t, J = 7.1 Hz, CH₃), 1.27 (12 H, t, J = 7.1 Hz, CH₃), 4.06–4.16

(16 H, m, CH₂), 7.85–7.98 (10 H, m, (EtO)₂OP-Ph), 8.00–8.06 (6

H, m, (EtO)₂OP-Ph), 8.25 (1 H, d, J = 4.7 Hz, H_β), 8.31 (1 H, d, J =

4.7 Hz, H_β), 8.34 (1 H, d, J = 4.7 Hz, H_β), 8.47 (1 H, d, J = 4.7 Hz,

H_β), 8.55 and 8.59 (2 H, AB system, J = 4.4 Hz, H_β) ppm. NH

protons are not observed. δ_P(202 MHz; CDCl₃; 25 °C: 18.76 (1

P), 18.81 (1 P), 18.96 (1 P), 19.22 (1 P) ppm. HRMS (ESI+): m/z

calcd for (C₅₉H₆₅N₄O₁₄P₄)⁺: 1177.34422; found: 1177.34304

[M+H]⁺; m/z calcd for (C₅₉H₆₄N₄NaO₁₄P₄)⁺: 1199.32617; found:

1199.32381 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 281 (3.62), 419

(4.89), 520 (3.51), 558 (3.51), 590 (3.29), 644 (3.08). IR:

ν_max/cm^-13337 (w, NH), 2980 (m), 2930 (m), 1772 (s, C=O),

1726 (m, C=O), 1602 (m), 1564 (m), 1452 (m), 1391 (m), 1367

(w), 1240 (s, P=O), 1189 (w), 1162 (m, P-O), 1129 (s), 1097 (w),

1048 (m), 1016 (s, P-O), 955 (s), 793 (s), 765 (s), 716 (s), 578

(s).

2,3-Dioxo-5,10,15,20-tetrakis(4-diethoxyphosphorylphenyl)-

chlorin (2H-6e)

The photooxidation of 2-aminoporphyrin 2H-2e according to

this procedure yields a complex mixture of products in which

target 2,3-dioxochlorin 2H-6e is presented in low ratio

according to MALDI-TOF analysis. Our attempts of its isolation

by column chromatography on silica or alumina were

unsuccessful. An effective procedure is given below.

A solution of Dess-Martin periodinane (55 µL of 0.3 M solution

in CH₂Cl₂, 0.0166 mmol) was added to a solution of porphyrin

2H-2e (15 mg, 0.0128 mmol) in degassed CH₂Cl₂(3 mL) under

N₂atmosphere. The reaction mixture was stirred at r.t. when

monitored by MALDI spectrometry. After 2 h the reaction

mixture was diluted with CH₂Cl₂(15 mL). The reaction mixture

was treated with 10 mL of 1M HCl and stirred for 20 min. The

organic layer was separated, washed with aqueous solution of

sodium carbonate (10 mL x 2) and water (10 mL), and dried

over anhydrous sodium sulfate. The solvent was removed

under reduced pressure and the residue was

chromatographed on alumina using a CH₂Cl₂/MeOH (99:1)

mixture as eluent. The product 2H-6e (15 mg, 99%) was

obtained as a brown solid.

General procedure for the preparation of imidazoporphyrins 2H-

14-19.⁴⁵

2,3-Dioxo-5,10,15,20-tetraarylchlorin 2H-6 (0.1 mmol) was

dissolved in chloroform (20 mL). Aldehyde 8-13 (0.5 mmol),

ammonium acetate (770 mg, 10 mmol) and trifluoroacetic acid

(200 μL) were added to this solution. The reaction mixture was

stirred at reflux and monitored by TLC. On the completion of

the condensation (3-7 h), the reaction mixture was washed

with water (20 mL x 2). The organic phase was separated and

dried over anhydrous sodium sulfate. The solution was

evaporated under reduced pressure and the residue was

δ_H(300 MHz; CDCl₃; 25 °C) -2.12 (2 H, br s, internal NH), 1.47

(12 H, t, J = 7.1 Hz, CH₃), 1.49 (12 H, t, J = 7.1 Hz, CH₃), 4.25-

4.43 (16 H, m, CH₂), 7.99 (4 H, dd, J = 8.3 Hz, J_HP= 4.1 Hz,

(EtO)₂OP-Ph_ortho), 8.09–8.23 (12 H, m, 4 H (EtO)₂OP-Ph_orthoand

8 H (EtO)₂OP-Ph_meta), 8.51 (2 H, s, 12,13-H_β), 8.56–8.60 (2 H, br

d, J = 5.0 Hz, 8,17-H_β), 8.71–8.75 (2 H, br d, J = 5.0 Hz, 7,18-H_β)

ppm. δ_P(121 MHz; CDCl₃; 25 °C) 18.26 (2 P), 18.75 (2 P) ppm.

HRMS (ESI+): m/z calcd for (C₆₀H₆₄N₄NaO₁₄P₄)⁺: 1211.32617;

found: 1211.32397 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 404 (5.18),

524 (3.98), 562 (3.92), 600 (3.84), 652 (3.88). IR: ν_max/cm^-1

3348 (w, NH), 2923 (m), 2853 (m), 2849 (m), 1734 (m), 1657

(w), 1632 (w), 1602 (w), 1456 (w), 1258 (m), 1017 (s), 971 (s),

796 (s), 580 (s), 558 (s).

purified by silica gel column chromatography using

hexane/CH₂Cl₂(1:1) (2H-14 2H-15) or CH₂Cl₂/MeOH (99:1)

2H-16 19) mixture to afford imidazoporphyrins 2H-14-19.

a

,

(

-

2-(4-Bromophenyl)-1H-imidazo[4,5-b]-5,10,15,20-

tetratolylporphyrin (2H-14a) was obtained from 2,3-dioxo-

5,10,15,20-tetratolylchlorin (2H-6a) and 4-bromobenzaldehyde

(8) in 90 % (78 mg) yield.

δ_H(300 MHz; CDCl₃; 25 °C) -2.92 (2 H, br s, internal NH), 2.70 (6

H, s, CH₃), 2.75 (3 H, s, CH₃), 2.81 (3 H, s, CH₃), 7.55 (4 H, br d, J

= 7.8 Hz, Tol_meta), 7.59 (4 H, br s, Br-Ph), 7.61 (2 H, d, J = 7.8 Hz,

Tol_meta), 7.73 (2 H, d, J = 7.8 Hz, Tol_meta), 8.10 (4 H, d, J = 7.8 Hz,

Tol_ortho), 8.14 (2 H, d, J = 7.8 Hz, Tol_ortho), 8.15 (2 H, d, J = 7.8 Hz,

Tol_ortho), 8.54 (1 H, br s, imidazole NH), 8.79 (2 H, s, H_β), 8.90 (1

H, d, J = 4.8 Hz, H_β), 8.93 and 8.96 (2 H, AB system, J_AB= 4.8 Hz,

H_β), 8.96 (1 H, d, J = 4.8 Hz, H_β) ppm. HRMS (ESI+): m/z calcd

for (C₅₅H₄₂BrN₆)⁺: 865.26488; found: 865.26391 [M+H]⁺.

λ_max(CHCl₃)/nm (log ε) 421 (5.25), 518 (4.15), 552 (3.83), 588

(3.77), 647 (3.25). IR: ν_max/cm^-13437 (w, NH), 3330 (w, NH),

2923 (m), 2852 (m), 2603 (m), 2497 (m), 1722 (m), 1471 (m),

1456 (m), 1398 (m), 1381 (m), 1267 (s), 1247 (m), 1181 (m),

1172 (m), 1163 (m), 1102 (m), 1072 (m), 1037 (m), 1019 (m),

1010 (m), 995 (w), 979 (m), 965 (m), 905 (w), 852 (m), 831 (m),

800 (s), 753 (s), 730 (s).

Procedure for the preparation of 2-oxa-3-oxo-5,10,15,20-

tetrakis(4-diethoxyphosphorylphenyl)chlorin (2Н-7е).

Silica gel (57 mg) was added to a solution of 2-aminoporphyrin

2H-2e (15 mg, 0.0128 mmol) in CH₂Cl₂(15 ml). The reaction

mixture was stirred under irradiation (Luzchem Ring

Illuminator) in the open flask and monitored by MALDI-TOF

spectrometry. After 2 h of the irradiation no more starting

material was observed and the lamp was switched off. The

reaction mixture was stirred for 8 h before an additional

portion (1.5 g) of silica gel was added and the reaction mixture

was evaporated under reduced pressure to dryness. The

residue was loaded on a top of an alumina column. The

12 | New J. Chem., 2016, 00, 1-3

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DOI: 10.1039/C5NJ03247D

ARTICLE

2-(4-Bromophenyl)-1H-imidazo[4,5-b]-5,10,15,20-

tetramesitylporphyrin (2H-14b) was obtained from 2,3-dioxo- 418 (5.29), 514 (4.25), 588 (3.81), 642 (3.49).

found: 1080.89326 [M+H]⁺. λ_max(CHCl₃)/nm (log ε) 288 (3.96),

5,10,15,20-tetramesitylchlorin

(

2H-6b

)

and

4-

2-(4-Nitrophenyl)-1H-imidazo[4,5-b]-5,10,15,20-

bromobenzaldehyde (8) in 64% (62 mg) yield.

tetratolylporphyrin (2H-15a) was obtained from 2,3-dioxo-

5,10,15,20-tetratolylchlorin (2H-6a) (119 mg, 017 mmol) and

δ_H(300 MHz; CDCl₃; 25 °C) -2.70 (2 H, br s, internal NH), 1.84 (6

H, s, CH_3ortho), 1.85 (6 H, s, CH_3ortho), 1.86 (6 H, s, CH_3ortho), 1.87

(6 H, s, CH_3ortho), 2.62 (6 H, s, CH_3para), 2.67 (3 H, s, CH_3para), 2.74

(3 H, s, CH_3para), 7.27 (4 H, br s, Mes), 7.32 (2 H, br s, Mes), 7.48

(2 H, br s, Mes), 7.59 and 7.61 (4 H, AB system, J_AB= 8.4 Hz, Br-

Ph), 8.29 (1 H, br s, imidazole NH), 8.58 (2 H, s, H_β), 8.73 (1 H,

d, J = 4.8 Hz, H_β), 8.76–8.79 (2 H, 2d, J = 4.8 Hz, H_β), 8.84 (1 H,

4-nitrobenzaldehyde (9) in 55% (78 mg) yield.

δ_H(300 MHz; CDCl₃; 25 °C) -2.94 (2 H, br s, internal NH), 2.70 (6

H, s, CH₃), 2.77 (3 H, s, CH₃), 2.84 (3 H, s, CH₃), 7.54 (4 H, br d, J

= 7.8 Hz, Tol_meta), 7.62 (2 H, d, J = 7.8 Hz, Tol_meta), 7.75 (2 H, d, J

= 7.8 Hz, Tol_meta), 7.83 (2 H d, J = 8.7 Hz, Ph), 8.09 (4 H, d, J =

7.8 Hz, Tol_ortho), 8.15 (4 H, d, J = 7.8 Hz, Tol_ortho), 8.32 (2 H, d, J =

8.7 Hz, Ph), 8.65 (1 H, s, imidazole NH), 8.77 (2 H, s, 12,13-H_β),

8.92 and 8.98 (2 H, AB system, J = 5.0 Hz, H_β), 8.95 and 8.98 (2

H, AB system, J = 5.0 Hz, H_β) ppm. HRMS (ESI+): m/z calcd for

(C₅₅H₄₂N₇O₂)⁺: 832.33945; found: 832.33894 [M+H]⁺.

λ_max(CHCl₃)/nm (log ε) 424 (5.38), 519 (4.33), 554 (3.98), 587

(3.93), 647 (3.35). IR: ν_max/cm^-13430 (w, NH), 3325 (w, NH),

2956 (m), 2924 (s), 2855 (m), 1722 (s), 1601 (m), 1517 (m,

NO₂), 1457 (m), 1408 (m), 1378 (m, NO₂), 1344 (s), 1328 (m),

1267 (s), 1248 (s), 1182 (m), 1165 (m), 1102 (m), 1019 (m), 996

(m), 978 (m), 966 (m), 853 (m), 799 (s), 753 (m), 730 (s), 667

(m), 660 (m).

d,

J = 4.5 Hz, H_β) ppm. HRMS (ESI+): m/z calcd for

(C₆₃H₅₇BrN₆)⁺: 977.38009; found: 977.38819 [M+H]⁺.

λ_max(CHCl₃)/nm (log ε) 304 (4.30), 419 (5.44), 516 (4.25), 548

(3.75), 587 (3.82), 645 (3.24). IR: ν_max/cm^-13437 (w, NH), 3330

(w, NH), 2923 (m), 2852 (m), 2603 (m), 2497 (m), 1724 (m),

1611 (m), 1566 (m), 1555 (m), 1471 (m), 1454 (m), 1408 (m),

1377 (m), 1346 (m), 1269 (m), 1242 (m), 1214 (m), 1169 (m),

1149 (m), 1103 (m), 1074 (m), 1032 (w), 1010 (m), 996 (m),

969 (m), 947 (m), 908 (w), 881(w), 851 (m), 827 (m), 800 (s),

775 (w), 754 (s), 729 (s), 664 (m).

2-(4-Bromophenyl)-1H-imidazo[4,5-b]-5,10,15,20-tetrakis(4-

methylcarboxyphenyl)porphyrin (2H-14d) was obtained from

2,3-dioxo-5,10,15,20-tetrakis(4-methylcarboxyphenyl)-chlorin

2-(4-Carboxyphenyl)-1H-imidazo[4,5-b]-5,10,15,20-

tetramesitylporphyrin (2H-16b) was obtained from 2,3-dioxo-

(

2H-6d) (50 mg, 0.057 mmol) and 4-bromobenzaldehyde (

8) in

5,10,15,20-tetramesitylchlorin

(

2H-6b

)

and

4-

69% (41 mg) yield.

carboxybenzaldehyde (10) in 53% (52 mg) yield.

δ_H(600 MHz; CDCl₃; 25 °C) -2.95 (2 H, br s, internal NH), 4.10 (6

δ_H(300 MHz; CDCl₃; 25 °C) -2.69 (2 H, br s, internal NH), 1.85 (s,

24 H, m, CH_3ortho), 2.62 (6 H, s, CH_3para), 2.68 (3 H, s, CH_3para),

2.76 (3 H, s, CH_3para), 7.27 (4 H, s, Mes), 7.33 (2 H, s, Mes), 7.49

(2 H, s, Mes), 7.79 (2 H, d, J = 8.5 Hz, HO₂C-Ph), 8.18 (2 H, d, J =

8.5 Hz, HO₂C-Ph), 8.39 (1 H, br s, imidazole NH), 8.57 (2 H, s,

H_β), 8.73 and 8.80 (2 H, AB system, J_AB= 4.6 Hz, H_β), 8.78 and

8.85 (2 H, AB system, J_AB= 4.6 Hz, H_β) ppm. HRMS (ESI+): m/z

calcd for (C₆₄H₅₉N₆O₂)⁺: 943.46940; found: 943.46891 [M+H]⁺.

λ_max(CHCl₃)/nm (log ε) 421 (5.37), 516 (4.23), 548 (3.78), 587

(3.82), 647 (3.34). IR: ν_max/cm^-13418 (w, NH), 3323 (w, NH),

2951 (w), 2917 (m), 2854 (m), 1687 (s, C=O), 1683 (m), 1611

(m), 1568 (w), 1447 (m), 1377 (m), 1284 (m), 1242 (m), 1215

(m), 1170 (m), 1150 (m), 1107 (w), 1031 (w), 1015 (m), 996

(m), 969 (m), 948 (m), 851 (m), 826 (m), 799 (s), 776 (m), 725

(s), 708 (s).

H, s, CH₃), 4.13 (3 H, s, CH₃), 4.17 (3 H, s, CH₃), 7.53 and 7.59 (4

H, AB system, J_AB= 8.4 Hz, Br-Ph), 8.28 (4 H_A, AB system, J_AB

=

8.3 Hz, MeCO₂-Ph_ortho), 8.33 (2 H, d, J = 7.9 Hz, MeCO₂-Ph_ortho),

8.36 (2 H, d, J = 7.9 Hz, MeCO₂-Ph_ortho), 8.43 (4 H_B, AB system,

J_AB= 8.3 Hz, MeCO₂-Ph_meta), 8.49 (2 H, d, J = 7.9 Hz, MeCO₂-

Ph_meta), 8.60 (3 H, br d, J = 7.9 Hz, imidazole NH and MeCO₂-

Ph_metha), 8.73 (2 H, s, 12,13-H_β), 8.81 (1 H, d, J = 4.8 Hz, 7-H_β),

8.88 (2 H, br s, H_β), 8.90 (1 H, d, J = 4.8 Hz, H_β) ppm. HRMS

(ESI+): m/z calcd for (C₅₉H₄₂BrN₆O₈)⁺: 1041.22420; found:

1041.22460 [M+H]⁺. λ_max(CHCl₃)/nm (log ε) 291 (4.48), 421

(5.51), 517 (4.33), 550 (3.90), 588 (3.90), 645 (3.39). IR:

ν_max/cm^-13437 (w, NH), 2957 (m), 2928 (m), 2859 (m), 1718 (s,

C=O), 1605 (m), 1504 (w), 1463 (m), 1433 (m), 1407 (m), 1382

(m), 1265 (s), 1247 (s), 1165 (w), 1113 (s), 1100 (s), 1019 (m),

995 (w), 961 (m), 874 (m), 818 (m), 795 (m), 764 (m), 729 (s).

2-(4-Carboxyphenyl)-1H-imidazo[4,5-b]-5,10,15,20-tetrakis(4-

bromophenyl)porphyrin (2H-16c) was obtained from 2,3-

2-(4-Bromophenyl)-1H-imidazo[4,5-b]-5,10,15,20-tetrakis(2,6-

dichlorophenyl)porphyrin (2H-14f) was obtained from 2,3-

dioxo-5,10,15,20-tetrakis(4-bromophenyl)chlorin

(2H-6c) (27

Dioxo-5,10,15,20-tetrakis(2,6-dichlorophenyl)chlorin

(

2H-6f

)

mg, 0.028 mmol) and 4-carboxybenzaldehyde (10) in 56% (17

mg) yield.

(18 mg, 0.02 mmol) and 4-bromobenzaldehyde (

mg) yield.

8) in 51% (11

δ_H(300 MHz; DMSO; 25 °C) -3.06 (2 H, br s, internal NH), 7.90–

8.20 (20 H, m, Br-Ph and HO₂C-Ph), 8.77 (2 H, br s, 12,13-H_β),

8.74–8.83 (2 H, m, 7,18-H_β), 8.88 (2 H, m, 8,17-H_β) ppm. HRMS

(ESI+): m/z calcd for (C₅₂H₃₁Br₄N₆O₂)⁺: 1086.92365; found:

1086.92570 [M+H]⁺. λ_max(CHCl₃)/nm (log ε) 420 (5.50), 517

(4.29), 551 (3.93), 588 (3.89), 649 (3.59). IR: ν_max/cm^-13450 (w,

NH), 3300 (w, NH), 2961 (m), 2920 (m), 2851 (m), 1692 (s,

C=O), 1610 (m), 1555(m), 1470 (m), 1375 (m), 1259 (s), 1202

δ_H(600 MHz; CDCl₃; 25 °C) -2.72 (2 H, br s, internal NH), 7.59

and 7.60 (4 H, AB system, J_AB= 8.7 Hz, Br-Ph), 7.69 (2 H, t, J =

8.4 Hz, Cl₂Ph_para), 7.74 (1 H, t, J = 8.4 Hz, Cl₂Ph_ortho), 7.79 (4 H,

d, J = 8.4 Hz, o-Cl₂Ph_meta), 7.82 (2 H, d, J = 8.4 Hz, o-Cl₂Ph_meta),

7.89 (1 H, t, J = 8.4 Hz, o-Cl₂Ph_ortho), 7.97 (2 H, d, J = 8.4 Hz, o-

Cl₂Ph_meta), 8.50 (1 H, br s, imidazole NH), 8.61 (2 H, s, 12,13-

H_β), 8.76-8.82 (3 H, br s, H_β), 8.87 (1 H, d, J = 4.8 Hz, H_β) ppm.

HRMS (ESI+): m/z calcd for (C₅₁H₂₆BrCl₈N₆)⁺: 1080.89051;

New J. Chem., 2016, 00, 1-3 | 13

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New Journal of Chemistry

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DOI: 10.1039/C5NJ03247D

ARTICLE

Journal Name

(m), 1165 (m), 1094 (m), 1069 (m), 1011 (s), 976 (m), 963 (m), 8.17 (2 H, d, J = 7.9 Hz), 8.19 (2 H, d, J = 7.9 Hz, Tol_ortho), 8.66 (1

H, br s, imidazole NH), 8.70 (2 H, ddd, ³J = 8.0 Hz, ⁴J = 1.1 Hz, ⁵J

793 (s), 750 (m), 725 (m), 680 (w).

3

4

= 1.0 Hz, terpyridine 3, 3’’ H), 8.77 (2 H, ddd, J = 4.8 Hz, J =

1.8 Hz, ⁵J = 0.9 Hz, terpyridine 6, 6’’ H), 8.79 (2 H, s, terpyridine

3’, 5’ H), 8.82 (2 H, s, H_β), 8.93 and 8.97 (2 H, AB system, J = 4.8

Hz, H_β), 8.93 and 8.98 (2 H, AB system, J = 4.8 Hz, H_β) ppm.

HRMS (ESI+): m/z calcd for (C₇₀H₅₂N₉)⁺: 1018.43402; found:

1018.43379 [M+H]⁺. λ_max(CHCl₃)/nm (log ε) 422 (5.12), 518

(3.95), 552 (3.64), 588 (3.57), 648 (3.27). IR: ν_max/cm^-13444 (w,

NH), 3330 (w, NH), 2954 (w), 2922 (m), 2852 (m), 1717 (m),

1604 (m), 1584 (m), 1568 (m), 1467 (m), 1390 (m), 1268 (m),

1246 (m), 1214 (m), 1181 (m), 1115 (m), 1038 (m), 1019 (m),

979 (m), 966 (m), 853(m), 791 (s), 752 (s), 732 (s), 667 (m), 660

(m).

2-(4-Carboxyphenyl)-1H-imidazo[4,5-b]-5,10,15,20-tetrakis(4-

diethoxyphosphorylphenyl)porphyrin (2H-16e) was obtained

from

2,3-dioxo-5,10,15,20-tetrakis(4-diethoxyphosphoryl-

2H-6e (34 mg, 0.029 mmol) and 4-

phenyl)chlorin

(

)

carboxybenzaldehyde (10) in 50% (19 mg) yield.

δ_H(300 MHz; CDCl₃; 25 °C) -2.97 (2 H, br s, internal NH), 1.46–

1.56 (24 H, m, CH₃), 4.30–4.46 (16 H, m, CH₂), 7.66 (2 H, d, J =

7.7 Hz, HO₂C-Ph), 8.04 (2 H, d, J = 7.7 Hz, HO₂C-Ph), 8.22 (6 H,

dd, J_PH= 12.9 Hz, J = 7.8 Hz, (EtO)₂OP-Ph_meta), 8.27–8.43 (10 H,

m, 2H (EtO)₂OP-Ph_metaand 8H (EtO)₂OP-Ph_ortho), 8.73 (2 H, s,

12,13-H_β), 8.92 (4 H, br s, 7,8,17,18-H_β) ppm. δ_P(121 MHz;

CDCl₃; 25 °C) 17.95 (1 P), 18.73 (2 P), 19.62 (1 P) ppm. HRMS

(ESI+): m/z calcd for (C₆₈H₇₁N₆O₁₄P₄)⁺: 1319.39732; found: Imidazo[4,5-b]porphyrin 2H-18b was obtained from 2,3-

1319.39772 [M+H]⁺; m/z calcd for (C₆₈H₇₀N₆NaO₁₄P₄)⁺: dioxo-5,10,15,20-tetramesitylchlorin

(2H-6b) (81 mg, 0.1

1341.37927; found: 1341.37905 [M+Na]⁺. λ_max(CHCl₃)/nm (log mmol) and 4’-(4-formylphenyl)-2,2’:6’,2’’-terpyridine (12) in

ε) 421 (5.35), 517 (4.20), 549 (3.82), 587 (3.82), 645 (3.41). IR: 48% (54 mg) yield.

ν_max/cm^-13418 (w, NH), 3323 (w, NH), 2956 (m), 2924 (m), δ_H(300 MHz; CDCl₃; 25 °C) -2.66 (2 H, br s, internal NH), 1.85-

2852 (m), 1716 (m), 1699 (m, C=O), 1601 (m), 1456 (m), 1393 1.91 (24 H, m, CH_3ortho), 2.63 (6 H, s, CH_3para), 2.73 (3 H, s,

(m), 1246 (m, P=O), 1165 (m, P–O), 1129 (m), 1100 (m), 1049 CH_3para), 2.82 (3 H, s, CH_3para), 7.28 (4 H, br s, Mes), 7.37 (2H, br

4

(s), 1018 (s), 991 (s, P–O), 794 (m), 759 (m), 730 (m), 667 (w).

s, Mes), 7.40 (2 H, ddd, ³J = 7.4 Hz, ³J = 4.8 Hz, J = 1.2 Hz,

terpyridine 5, 5’’ H), 7.53 (2 H, br s, Mes), 7.88 (2 H, d, J = 8.6

3

Hz, Ph), 7.92 (2 H, ddd, J = 7.5 Hz, ³J = 8.0 Hz, ⁴J = 1.8 Hz,

2-(4-Diethoxyphosphorylphenyl)-1H-imidazo[4,5-b]-

5,10,15,20-tetramesitylporphyrin (2H-17b) was obtained from

2,3-dioxo-5,10,15,20-tetramesitylchlorin (2H-6b) (292 mg, 0.36

mmol) and 4-diethoxyphosphorylbenzaldehyde (11) in 71%

(264 mg) yield.

terpyridine 4, 4’’ H), 8.07 (2 H, d, J = 8.6 Hz, Ph), 8.42 (1 H, br s,

imidazole NH), 8.60 (2 H, s, terpyridine 3’,5’ H), 8.72 (2 H, ddd,

³J = 8.0 Hz, ⁴J = 1.1 Hz, ⁵J = 1.0 Hz, terpyridine 3, 3’’ H), 8.75 and

8.82 (2 H, AB system, J = 4.8 Hz, H_β), 8.79 (2 H, ddd, ³J = 4.8 Hz,

⁴J = 1.8 Hz, ⁵J = 0.9 Hz, terpyridine 6, 6’’ H), 8.80 and 8.87 (2 H,

AB system, J = 4.8 Hz, H_β), 8.84 (2 H, s, 12,13-H_β) ppm. HRMS

(ESI+): m/z calcd for (C₇₈H₆₈N₉)⁺: 1130.55922; found:

1130.55895 [M+H]⁺. λ_max(CHCl₃)/nm (log ε) 421 (5.39), 517

(4.26), 548 (3.81), 587 (3.84), 646 (3.47). IR: ν_max/cm^-13415 (w,

NH), 3309 (w, NH), 2920 (m), 2852 (m), 1719 (m), 1604 (m),

1584 (m), 1567 (m), 1467 (m), 1443 (m), 1390 (m), 1378 (m),

1266 (m), 1247 (m), 1214 (m), 1170 (m), 1149 (m), 1115 (m),

1102 (m), 1037 (m), 1017 (m), 994 (m), 970 (m), 947 (m), 851

(m), 827 (m), 793 (s), 729 (s), 709 (m), 692 (m), 660 (m).

δ_H(300 MHz; CDCl₃; 25 °C) -2.69 (2 H, br s, internal NH), 1.83 (6

H, s, CH_3ortho), 1.85 (12 H, s, CH_3ortho), 1.86 (6 H, s, CH_3ortho), 2.61

(6 H, s, CH_3para), 2.67 (3 H, s, CH_3para), 2.75 (3 H, s, CH_3para),

4.04–4.25 (4 H, m, CH₂), 7.26 (4 H, br s, Mes), 7.32 (2 H, s,

Mes), 7.48 (2 H, s, Mes), 7.78 (2 H, dd, J = 8.3 Hz, J_PH= 3.8 Hz,

(EtO)₂OP-Ph_ortho), 7.90 (2 H, dd, J_PH= 12.7 Hz, J = 8.3 Hz,

(EtO)₂OP-Ph_meta), 8.36 (1 H, br s, imidazole NH), 8.57 (2 H, s,

12,13-H_β), 8.72 and 8.78 (2 H, AB system, J_AB= 4.8 Hz, 17,18-

H_β), 8.78 and 8.84 (2 H, AB system, J_AB= 4.8 Hz, 8,7-H_β) ppm.

δ_P(121 MHz; CDCl₃; 25 °C) 18.31 (1 P, s) ppm. HRMS (ESI+): m/z

calcd for (C₆₇H₆₈N₆O₃P)⁺: 1035.50850; found: 1035.50934

[M+H]⁺. λ_max(CHCl₃)/nm (log ε) 421 (5.35), 517 (4.22), 548 Imidazo[4,5-b]porphyrin 2H-19a was obtained from 2,3-dioxo-

(3.75), 587 (3.77), 647 (3.24). IR: ν_max/cm^-13418 (w, NH), 3323 5,10,15,20-tetratolylchlorin (2H-6a) (70 mg, 0.1 mmol) and 4’-

(w, NH), 2957 (m), 2925 (m), 2859 (m), 1720 (s), 1606 (w), formylbenzo-15-crown-5 (13) in 50% (49 mg) yield.

1506 (w), 1458 (m), 1408 (m), 1379 (m), 1265 (s), 1247 (s, δ_H(300 MHz; CDCl₃; 25 °C) -2.90 (2 H, br s, internal NH), 2.70 (6

P=O), 1171 (m, P–O), 1115 (s), 1101 (s), 1019 (m), 969 (m, P– H, s, CH₃), 2.73 (3 H, s, CH₃), 2.80 (3 H, s, CH₃), 3.77-3.88 (8 H,

O), 874 (m), 801 (m), 729 (s).

m, CH₂), 3.91–3.97 (2 H, m, CH₂), 4.01–4.07 (2 H, m, CH₂),

4.16–4.22 (2 H, m, CH₂), 4.26-4.32 (2 H, m, CH₂), 6.92 (1 H, d, J

= 8.2 Hz, Ph), 7.09 (1 H, dd, ³J = 8.2, ⁴J = 2.0 Hz, Ph), 7.54 (1 H,

d, ⁴J = 2.0 Hz, Ph), 7.55 (4 H, d, J = 7.9 Hz, Tol_meta), 7.62 (2 H, d,

J = 8.0 Hz, Tol_meta), 7.72 (2 H, d, J = 8.0 Hz, Tol_meta), 8.11 (4 H, d,

J = 7.9 Hz, Tol_ortho), 8.15 (2 H, d, J = 8.0 Hz, Tol_ortho), 8.19 (2 H, d,

J = 8.0 Hz, Tol_ortho), 8.53 (1 H, br s, imidazole NH), 8.81 (2 H, s,

12,13-H_β), 8.91 and 8.96 (2 H, AB system, J = 4.9 Hz, H_β), 8.94

and 9.00 (2 H, AB system, J_AB= 4.9 Hz, H_β) ppm. HRMS (ESI+):

m/z calcd for (C₆₃H₅₇N₆O₅)⁺: 977.43850; found: 977.43951

[M+H]⁺; m/z calcd for (C₆₃H₅₆N₆NaO₅)⁺: 999.42044; found:

999.41570 [M+Na]⁺. λ_max(CHCl₃)/nm (log ε) 420 (5.44), 518

Imidazo[4,5-b]porphyrin (2H-18a) was obtained from 2,3-

dioxo-5,10,15,20-tetratolylchlorin (2H-6a) (70 mg, 0.1 mmol)

and 4’-(4-formylphenyl)-2,2’:6’,2’’-terpyridine (12) in 49% (50

mg) yield.

δ_H(300 MHz; CDCl₃; 25 °C) -2.91 (2 H, br s, internal NH), 2.70 (6

H, s, CH₃), 2.80 (3 H, s, CH₃), 2.87 (3 H, s, CH₃), 7.38 (2 H, ddd, ³J

= 7.6 Hz, ³J = 4.8 Hz, ⁴J = 1.2 Hz, terpyridine 5, 5’’ H), 7.55 (4 H,

d, J = 7.9 Hz, Tol_meta), 7.65 (2 H, d, J = 7.9 Hz, Tol_meta), 7.77 (2 H,

d, J = 7.9 Hz, Tol_meta), 7.87 (2 H, d, J = 8.6 Hz, Ph), 7.90 (2 H,

3

4

ddd, J = 7.9 Hz, J = 7.6 Hz, J = 1.8 Hz, terpyridine 4, 4’’ H),

8.05 (2 H, d, J = 8.6 Hz, Ph), 8.10 (4 H, d, J = 7.9 Hz, Tol_ortho),

14 | New J. Chem., 2016, 00, 1-3

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(4.26), 552 (3.91), 588 (3.84), 647 (3.55). IR: ν_max/cm^-13439 (w, and 2.0 M solution of DIEA in NMP (25 μL, 50

ꢀ

mol, 5 equiv).

NH), 3316 (w, NH), 2920 (m), 2853 (m), 1721 (m), 1607 (w), The resulting reaction mixture was stirred at r.t. for 30 min.

1448 (m), 1406 (w), 1350 (w), 1267 (s), 1247 (m), 1217 (m), The reaction progress was monitored by ESI-MS and the

1182 (m), 1161 (m), 1136 (m), 1115 (m), 1053 (m), 1021 (m), reactions were stopped after a full consumption of the starting

996 (m), 977 (m), 964 (m), 935 (m), 881 (w), 826 (m), 796 (s), acid. The NHS esters were characterized by ESI-MS.

752 (m), 729 (s), 648 (m).

2H-22b: LRMS (ESI+): m/z calcd for (C₆₈H₆₂N₇O₄)⁺: 1040.49;

[2-(4-Carboxyphenyl)-1H-imidazo[4,5-b]-5,10,15,20-

found: 1040.55 [M+H]⁺.

tetramesitylporphyrinato]zinc (Zn-16b) was prepared by Zn-22b: LRMS (ESI+): m/z calcd for (C₆₈H₆₀N₇O₄Zn)⁺: 1102.40;

metallation of 2H-16b (86 mg, 0.09 mmol) by Zn(OAc)₂(5 found: 1102.55 [M+H]⁺.

equiv) in CHCl₃/MeOH (9:1) in 85% (78 mg) yield.

Zn-22e: MS (ESI-): m/z calcd for (C₇₂H₇₁N₇O₁₆P₄Zn): 1477.32;

δ_H(300 MHz; CDCl₃; 25 °C) 1.84 (12 H, 2, CH_3ortho), 1.85 (12 H, 2, found: 1478.40 [M+1]^-, LRMS (ESI+): m/z calcd for

CH_3ortho), 2.62 (6 H, s, CH_3para), 2.65–2.80 (6 H, 2 br s, CH_3para), (C₇₂H₇₁N₇O₁₆P₄Zn): 1477.32; found: 1502.33 [M+Na+1]⁺.

7.26 (4 H, s, Mes), 7.29–7.38 (2 H, br s, Mes), 7.43-7.53 (2 H, br

2H-21e: Porphyrin carboxylic acid 2H-5e (22 mg, 17

ꢀmol)

s, Mes), 7.84 (2 H, d, J = 8.4 Hz, Ph), 8.18 (2 H, d, J = 8.4 Hz, Ph),

8.52 (1 H, br s, imidazole NH), 8.69 (2 H, s, 12,13-H_β), 8.73-8.88

(4 H, br s, 7,8,17,18-H_β) ppm. HRMS (ESI+): m/z calcd for

(C₆₄H₅₇N₆O₂Zn)⁺: 1005.38290; found: 1005.38351 [M+H]⁺.

λ_max(CHCl₃)/nm (log ε) 429 (5.39), 552 (4.20), 590 (3.90), 620

(3.56). IR: ν_max/cm^-13410 (w, NH), 2915 (m), 2851 (m), 1721

(s), 1692 (s), 1610 (s), 1572(w), 1434 (m), 1375 (w), 1257 (s),

1190 (m), 1097 (m), 993 (s), 951 (w), 852 (w), 796 (m), 752 (m),

724 (m), 555 (w).

were also reacted with TSTU under these conditions. However,

the target product was not detected because imide 2H-21e

was formed in the intermolecular acylation reaction. The

reaction mixture was subjected to column chromatography on

silica gel using gradual CH₂Cl₂/MeOH (0-5%) system as an

eluent. Yield 42% (9 mg).

δ_H(300 MHz; CDCl₃; 25 °C) -2.83 (2 H, br s, internal NH), 1.46–

1.54 (24 H, m, CH₃), 2.86 (4 H, s, CH₂-CH₂), 4.27–4.44 (16 H, m,

CH₂), 8.11 (2 H, dd, J_PH= 13.1 Hz, J = 8.1 Hz, (EtO)₂OP-Ph_meta),

8.17 (2 H, dd, J_PH= 13.1 Hz, J = 8.1 Hz, (EtO)₂OP-Ph_meta), 8.19 (2

H, dd, J_PH= 13.1 Hz, J = 8.1 Hz, (EtO)₂OP-Ph_meta), 8.20 (2 H, dd,

[2-(4-Carboxyphenyl)-1H-imidazo[4,5-b]-5,10,15,20-

tetrakis(4-diethoxyphosphoryl)porphyrinato]zinc

was prepared by metallation of 2H-16e (66 mg, 0.05 mmol) by Hz, J_PH= 3.9 Hz, (EtO)₂OP-Ph_ortho), 8.28 (2 H, dd, J = 8.2 Hz, J_PH

Zn(OAc)₂(5 equiv) in CHCl₃/MeOH (9:1) in 89% (61 mg) yield. 3.9 Hz, (EtO)₂OP-Ph_ortho), 8.31 (4 H, 2dd, J = 8.2 Hz, J_PH=3.9 Hz,

(Zn-16e) J_PH= 13.1 Hz, J = 8.1 Hz, (EtO)₂OP-Ph_meta), 8.22 (2 H, dd, J = 8.2

=

δ_H(500 MHz; CDCl₃/MeOH (2:1); 25 °C) 1.30 (12 H, t, J = 7.1 Hz, (EtO)₂OP-Ph_ortho), 8.61 (1 H, s, 3-H_β), 8.62 (1 H, d, J = 5.0 Hz, 8-

CH₃), 1.33 (12 H, t, J = 7.1 Hz, CH₃), 4.09–4.28 (16 H, m, CH₂), H_β), 8.71 and 8.72 (2 H, AB system, J_AB= 4.9 Hz, 17,18-H_β), 8.78

7.63 (2 H, d, J = 8.4 Hz, HO₂C-Ph), 7.91 (2 H, d, J = 8.4 Hz, HO₂C- (1 H, d, J = 5.0 Hz, 7-H_β), 8.85 (2 H, br s, 12,13-H_β) ppm. δ_P(121

Ph), 7.95 (4 H, dd, J_PH= 13.2 Hz, J = 7.9 Hz, (EtO)₂OP-Ph_meta), MHz; CDCl₃; 25 °C) 17.83 (1 P), 18.52 (1 P), 18.60 (2 P) ppm.

8.07 (4 H, dd, J_PH= 13.2 Hz, J = 7.9 Hz, (EtO)₂OP-Ph_meta), 8.14 (4 HRMS (ESI+): m/z calcd for (C₆₄H₇₀N₅O₁₄P₄)⁺: 1256.38642;

H, dd, J_PH= 4.0 Hz, J = 8.2 Hz, (EtO)₂OP-Ph_ortho), 8.23 (4 H, dd, found: 1256.38851 [M+H]⁺. λ_max(CHCl₃)/nm (log ε) 421 (5.59),

J_PH= 4.0 Hz, J = 8.2 Hz, (EtO)₂OP-Ph_ortho), 8.57 (2 H, d, J = 4.8 518 (4.12), 550 (3.72), 594 (3.59), 647 (3.50). IR: ν_max/cm^-1

Hz, H_β), 8.59 (2 H, s, H_β), 8.64 (2 H, d, J = 4.8 Hz, H_β) ppm. 3400 (br, OH), 3328 (w, NH), 2964 (m), 2931 (m), 2874 (m),

δ_P(121 MHz; CDCl₃/MeOH (2:1); 25 °C) 23.52 ppm. HRMS (ESI- 1717 (s, C=O), 1683 (s, C=O), 1600 (m), 1475 (m), 1444 (m),

): m/z calcd for (C₆₈H₆₇N₆O₁₄P₄Zn)^-: 1379.29627; found: 1389 (s), 1349 (m), 1238 (s, P=O), 1163 (m, P–O), 1128 (s),

1379.29754 [M-H]^-. λ_max(CH₂Cl₂)/nm (log ε) 318 (3.91), 430 1047 (s), 1016 (s), 960 (s, P–O), 796 (s), 761 (s), 581 (s).

(4.90), 560 (3.74), 598 (3.53). IR: ν_max/cm^-13354 (br, OH), 2977

Step II – General procedure for sulfonation of esters M-22.

(m), 2926 (m), 1700 (w), 1599 (m), 1475 (w), 1440 (w), 1389

(m), 1333 (w), 1228 (m), 1160 (m), 1130 (m), 1096 (w), 1013 To the solution of TBA salt of β-Ala(SO₃H) (20) in NMP (600 μL

(s), 938 (s), 763 (s), 725 (s), 637 (w), 578 (s), 455 (m).

of 0.25 M solution) was added with stirring a solution of DIEA

in NMP (40 μL of 2.0 M solution). The resulting solution was

cooled up to 4 °C. Then a solution of ester M-22 obtained in

the step I was added by portions. The resulting reaction

mixture was stirred at 4 °C for 15 min before to be warmed up

Sulfonation of carboxylic acid 2H-5 and M-16.

Porphyrin carboxylic acids were linked with β-Ala(SO₃H) (20)

according to the two-step procedure consisting of their to r.t.. The stirring was continued for 2 h. Then the product M-

transformation into reactive N-hydroxysuccinimidyl (NHS) was isolated by semi-preparative RP-HPLC.

esters followed by aminolysis by -Ala(SO₃H) (20).

3

β

2H-3b (purification by RP-HPLC with system A followed by

Step I – General procedure for the preparation of N-

hydroxysuccinimide esters M-22.

three freeze-drying processes)

δ_H(300 MHz; CDCl₃; 25 °C) -2.71 (2 H, br s, internal NH), 1.83

(12 H, s, CH_3ortho), 1.84 (12 H, s, CH_3ortho), 2.61 (6 H, s, CH_3para),

2.69 (6 H, s, CH_3para), 3.87–4.09 (2 H, m, CH₂), 4.29-4.46 (1 H,

m, CH), 7.25 (4 H, s, Mes), 7.38 (4 H, s, Mes), 7.73 (2 H, d, J =

8.3 Hz, Ph_meta), 7.87 (1 H, br s, NH), 7.92 (2 H, d, J = 8.3 Hz,

To a solution of porphyrin carboxylic acid M-16 (10 μmol) in

200 μL of N-methyl-2-pyrrolidone (NMP) were sequentially

added a solution of TSTU (10 μmol, 1 equiv) in 100 μL of NMP

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Ph_ortho), 8.29 (1 H, br s, imidazole NH), 8.56 (2 H, s, 12,13-H_β), and RAS. Prof R. Guilard acknowledges support from the

8.73 and 8.78 (4 H, 2 AB systems, J = 4.8 Hz, 7,8,17,18-H_β) ppm. French Academy of Sciences (Emile Jungfleisch Award). Prof. A.

HRMS (ESI+): m/z calcd for (C₆₇H₆₄N₇O₆S)⁺: 1094.46333; found: Romieu thanks the Institut Universitaire de France (IUF) and

1094.46406 [M+H]⁺; m/z calcd for (C₆₇H₆₃N₇NaO₆S)⁺: the Burgundy region ("FABER" programme, PARI Action 6,

1116.44527; found: 1116.44535 [M+Na]⁺. λ_max(CHCl₃)/nm (log SSTIC 6 "Imagerie, instrumentation, chimie et applications

ε) 421 (5.26), 515 (4.06), 550 (3.71), 589 (3.68), 648 (3.54). IR: biomédicales") for financial support.⁸⁹

ν_max/cm^-13416 (w, OH), 3330 (w, NH), 2955 (s), 2921 (s), 2853

(s), 1646 (m, C=O), 1611 (m), 1550 (m), 1456 (m), 1377 (m),

References

1214 (m, S=O), 1169 (m), 1038 (m, S=O), 969 (w), 947 (w), 852

(w), 801 (s), 753 (s), 664 (w).

1

J.-H. Chou, M. E. Kosal, H. S. Nalwa, N. A. Rakow and K. S.

Suslick, in The Porphyrin Handbook, eds. K. M. Kadish, K. M.

Smith and R. Guilard, Academic Press, San Diego, 2000, vol. 6,

pp. 43.

Zn-3b (purification by RP-HPLC with system B followed by

three freeze-drying processes)

δ_H(300 MHz; CDCl₃; 25 °C) 1.82 (12 H, s, CH_3ortho), 1.84 (12 H, s,

CH_3ortho), 2.61 (6 H, s, CH_3para), 2.71 (6 H, s, CH_3para), 3.85–4.00

(2 H, m, CH₂), 4.25–4.41 (1 H, m, CH), 7.25 (4 H, s, Mes), 7.38 (4

H, br s, Mes), 7.77 (2 H, d, J = 7.1 Hz, Ph_meta), 7.87–7.98 (3 H, m,

2 H Ph_ortho+ 1 H NH), 8.06 (1 H, s, imidazole NH), 8.67 (2 H, s,

12,13-H_β), 8.71–8.77 (2 H, br s, H_β), 8.77–8.84 (2 H, br s, H_β)

ppm. HRMS (ESI+): m/z calcd for (C₆₇H₆₂N₇O₆SZn)⁺:

1156.37683; found: 1156.37844 [M+H]⁺; m/z calcd for

(C₆₇H₆₁N₇NaO₆SZn)⁺: 1178.35877; found: 1178.35803 [M+Na]⁺.

λ_max(CHCl₃)/nm (log ε) 314 (4.54), 428 (5.72), 552 (4.41), 590

(4.09). IR: ν_max/cm^-13416 (br, OH), 2966 (m), 2917 (m), 2852

(m), 1724 (s), 1646 (s, C=O), 1611 (s), 1550 (w), 1552 (m), 1474

(m), 1453 (m), 1376 (w), 1327 (w), 1227 (w, S=O), 1189 (s),

1085 (w), 1037 (s, S=O), 992 (s), 877 (w), 854 (m), 830 (m), 796

(m), 753 (m), 726 (m), 623 (w), 557 (w).

2

J. A. A. W. Elemans, R. vanꢀHameren, R. J. M. Nolte and A. E.

Rowan, Adv. Mater., 2006, 18, 1251.

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4

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1.

M. K. Panda, K. Ladomenou and A. G. Coutsolelos, Coord. Chem.

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9

Q. Zha, X. Rui, T. Wei and Y. Xie, CrystEngComm, 2014, 16, 7371.

10 D. V. Konarev, S. S. Khasanov and R. N. Lyubovskaya, Coord.

Chem. Rev., 2014, 262, 16.

Zn-3e (purification by RP-HPLC with system C followed by

three freeze-drying processes)

11 M. da Vicente and K. M. Smith, Curr. Org. Synth., 2014, 11, 3.

12 M. G. H. Vicente, in The Porphyrin Handbook, eds. K. M. Kadish,

K. M. Smith and R. Guilard, Academic Press, San Diego, 2000,

vol. 1, pp. 149.

13 L. Jaquinod, in The Porphyrin Handbook, eds. K. M. Kadish, K. M.

Smith and R. Guilard, Academic Press, San Diego, 2000, vol. 1,

pp. 201.

14 E. V. Vinogradova, Y. Y. Enakieva, S. E. Nefedov, K. P. Birin, A. Y.

Tsivadze, Y. G. Gorbunova, A. G. Bessmertnykh-Lemeune, C.

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15 J.-i. Setsune, J. Porphyrins Phthalocyanines, 2004, 8, 93.

16 H. Shinokubo and A. Osuka, Chem. Commun., 2009, 1011.

δ_H(300 MHz; CDCl₃; 25 °C) 1.34–1.47 (24 H, m, CH₃), 3.85–3.93

(2 H, m, CH₂), 4.01–4.09 (1 H, m CH), 4.18-4.37 (16 H, m, CH₂),

7.68 and 7.74 (4 H, AB system, J_AB= 8.4 Hz, HNCO-Ph), 8.04 (4

H, dd, J_PH= 13.0 Hz, J = 7.9 Hz, (EtO)₂OP-Ph_meta), 8.09–8.20 (4

H, m, (EtO)₂OP-Ph_meta), 8.20-8.27 (4 H, m, (EtO)₂OP-Ph_ortho),

8.27–8.34 (4 H, m, (EtO)₂OP-Ph_ortho), 8.66–8.76 (6 H, m, H_β)

ppm. δ_P(121 MHz; CDCl₃; 25 °C) 23.52 (3 P, br s), 23.59 (1 P, br

s) ppm. HRMS (ESI): m/z calcd for (C₇₁H₇₄N₇O₁₈P₄SZn)⁺:

1532.30475; found: 1532.30150 [M+H]⁺; m/z calcd for

(C₇₁H₇₃N₇NaO₁₈P₄SZn)⁺: 1554.28669; found: 1554.28440 17 M. O. Senge, Chem. Commun., 2011, 47, 1943.

[M+Na]⁺. λ_max(PBS buffer)/nm 315, 406, 443, 563, 601. IR:

18 H. Yorimitsu and A. Osuka, Asian J. Org. Chem., 2013, 2, 356.

ν_max/cm^-13366 (br, OH), 2981 (m), 2934 (m), 2903 (m), 1644

19 H. J. Shine, A. G. Padilla and S.-M. Wu, J. Org. Chem., 1979, 44,

4069.

(m, C=O), 1598 (s), 1548 (w), 1525 (w), 1476 (w), 1441 (w),

20 A. Giraudeau, H. J. Callot, J. Jordan, I. Ezhar and M. Gross, J. Am.

1389 (m), 1227 (s, S=O), 1190 (s), 1161 (m), 1129 (m), 1044

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max 20 words

A two steps methodology to prepare a series of meso-tetraarylporphyrin conjugates bearing water-soluble

moieties, anchoring groups and receptor subunits.

colour graphic (8 x 4)

Article Doi

On the synthesis of functionalized porphyrins and porphyrin conjugates: Via β-aminoporphyrins

DOI: 10.1039/c5nj03247d

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Full text of DOI:10.1039/c5nj03247d

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