Soluble meso-tetrakis(arylethynyl)porphyrins - synthesis and optical properties

Journal of Porphyrins and Phthalocyanines

J. Porphyrins Phthalocyanines 2014; 18: 1–16

DOI: 10.1142/S1088424614500904

Published at http://www.worldscinet.com/jpp/

Soluble meso-tetrakis(arylethynyl)porphyrins — synthesis

and optical properties

Agnieszka Nowak-Król^a◊, Łukasz G. Łukasiewicz^a, Joy E. Haley^b,

Mikhail Drobizhev^c, Aleksander Rebane*^c,d◊, Thomas M. Cooper*^b

and Daniel T. Gryko*^a◊

^aInstitute of Organic Chemistry of the Polish Academy of Sciences, Kasprzaka 44/52, 01-224 Warsaw, Poland

^bAir Force Research Laboratory, Materials and Manufacturing Directorate, WPAFB OH 45458, USA

^cMontana State University, Department of Physics, Bozeman, MT 59717, USA

^dNational Institute of Chemical Physics and Biophysics, Tallinn, Estonia

Dedicated to Professor Nagao Kobayashi on the occasion of his 65th birthday

Received 6 August 2014

Accepted 16 September 2014

ABSTRACT: Trans-A₂B₂-tetrakis(arylethynyl)porphyrins with suitable solubility in CH₂Cl₂, CHCl₃,

EtOAc, acetone and toluene have been obtained for the ﬁrst time. Among two possible strategies the

one comprising the synthesis of 5,15-dibromo-10,20-bis[(isopropylsilyl)ethynyl]porphyrin proved to

be more efﬁcient. The pathway towards densely substituted arylacetylenes has been optimized. The

use of previously identiﬁed 3,4,5-trialkoxyaryl substituent was crucial for achieving the reasonable

solubility. The optical properties of meso-substituted tetrakis(arylethynyl)porphyrins were studied

showing that strong polarization imparted by direct conjugation of all four substituents with porphyrin

core resulted not only in strong absorption of red light but also in a relatively long triplet lifetime. Meso-

tetrakis(arylethynyl)porphyrins have a signiﬁcantly longer lifetime of T₁state than bis(arylethynyl)

porphyrins and in their case all the states are mixtures of transitions between the HOMO-1, HOMO and

LUMO, LUMO+1 MOs. We show that the presence of two additional arylethynyl substituents at meso-

positions enhance the maximum two-photon absorption cross-section of trans-A₂B₂-tetrakis(arylethynyl)

porphyrins by more than one order of magnitude. Maximum values as high as s₂= 500 GM at 950 nm

result from realization of suitable conditions for effective resonance enhancement along with a lowering

of the energy and intensiﬁcation of the two-photon allowed transitions in the Soret region.

KEYWORDS: porphyrins, alkynes, absorption, Sonogashira, triplet.

non-stopping attention of scientiﬁc community [2].

Conceptually, there are several approaches to reach this

goal without interfering in a construction of a porphyrin

INTRODUCTION

Since the mean angle between meso-aryl substituents

and porphyrin core is ~50°, alteration of these substituents

core, i.e. without changing the number of pyrrole subunits

has rather limited impact on porphyrin’s physicochemical

and methine bridges. The ﬁrst approach is based on

properties [1]. These properties, however, may be effecti-

placement of one or more fused aromatic or heteroaromatic

vely and widely tuned via extension of the porphyrin core.

rings at adjacent b-positions of the tetrapyrrolic macro-

Such p-extension of the porphyrin chromophore attracts

cycle [3]. Another route to gain extended p-system

arises from the fact that porphyrins are electron-rich

and as such may undergo inter- and intramolecular

^◊SPP full member in good standing

oxidative aromatic coupling [4]. A complementary idea

combines both aforementioned strategies i.e. elongation

*Correspondence to: Daniel T. Gryko, email: daniel.gryko@

icho.edu.pl, tel: +48 (22)-3433063, fax: +48 (22)-6326681

2

A. NOWAK-KRÓL ET AL.

O

of the porphyrin p-electron system is achieved by fusing

adjacent b substituents [5]. Still, among many options

which were explored in the last 30 years the extension

via triple bonds is conceptually perhaps the simplest.

This approach has been intensively explored over last

decades both theoretically and practically [6–8]. The

studies of bis(arylethynyl)porphyrins are widespread but

the synthesis and photophysical studies of compounds

possessing four arylethynyl groups at all meso-positions

are rare cases and only dozen papers have appeared

up-to-date on this topic [9]. Among them only ﬁve deal

with trans-A₂B₂-porphyrins of that type [10]. Very

poor solubility of these compounds and not the lack of

suitable synthetic methodologies is the crucial reason for

that situation. In this context, we wondered if using the

motive, which we identiﬁed in recent years to improve

solubility of porphyrins (and to reach liquidity at room

temperature) [11] would ﬁnally allow to obtain meso-

tetrakis(arylethynyl)porphyrins with sufﬁcient solubility.

P

TsN₃

+

EtO

OEt

1

91% NaH, THF

CHO

O

P

O

EtO

+

EtO

H₂₅C₁₂

O

OC₁₂H₂₅

N

OC₁₂H₂₅

3a

2

Cs₂CO₃, i-PrOH

19%

C₁₂H₂₅

O

OC₁₂H₂₅

RESULTS AND DISCUSSION

OC₁₂H₂₅

Initially we planned to obtain targeted porphyrins via

[2+2] condensation of 5-[3,4,5-tris(decyloxy)phenyl]

dipyrrane (7) with corresponding [tris(alkoxy)phenyl]

propynals. While the synthesis of dipyrrane 7 was

straightforward [13, 14], the preparation of arylpropargyl

aldehydes required an investigation of a few options.

Among various general strategies we decided to apply

the synthesis of arylalkynes from aromatic aldehydes.

One of the most efﬁcient general methods to achieve

this transformation is reaction of aldehydes with dialkyl

diazomethylphosphonates. In the presence of base,

these esters undergo deprotonation leading to unstable

diazoalkene followed by Horner–Wadsworth–Emmons

reaction with aldehydes. As originally observed by

groups of Seyferth [15], Gilbert [16] and Colvin [17]

the ﬁrst intermediate after thermal extrusion of N₂

gives carbene which ﬁnally undergoes rearrangement

into alkyne. We generated stable diethyl 1-diazo-

2-oxopropylphosphonate (2), in reaction of diethyl

2-oxopropylphosphonate (1) [18] with tosyl azide [18]

(Scheme 1).

4a

Scheme 1.

In the ﬁrst step, we transformed aldehyde 3a into

compound 5a via the reaction with triphenylphosphine

and tetrabromomethane (Scheme 2) [21]. Subsequent

elimination led directly to alkyne 4a. Although TLC

monitoringofthereactionmixtureshowedthatconversion

was full after 1h, substrate was still present and its

removal from product required careful chromatography.

Replacing of n-buthyllithium with t-BuOLi did not

improve the yield of alkyne 4a. Finally, a change of

substrate 3b combined with bigger excess of n-BuLi

and a longer reaction time allowed us to obtain alkyne

4b in satisfactory yield (Scheme 2). Unfortunately, when

aldehyde 3a was replaced with aldehyde 3c, possessing

tetraethyleneglycol chains, the yield of the corresponding

alkyne dropped to 12% (Scheme 2).

Only traces of alkyne 4a were observed in the

subsequent reaction with aldehyde 3a [11] following

conditions developed by Bestmann and co-workers

(MeOH, K₂CO₃) [19]. Both bad solubility of lypophilic

aldehyde 3a and its electron-rich (hence less reactive)

character plausibly contributed to this failure [20]. The

yield of 4a increased to 19% when MeOH was replaced

by i-PrOH, following the conditions published by Ghosh

(Scheme 1) [18]. Still, the reaction was very slow and

in order to increase conversion the large excess of both

base and phosphonate have been used. Not satisﬁed with

overall efﬁciency of this transformation we focused our

investigation on Corey–Fuchs method.

The next step towards targeted arylpropargylaldehydes

required formylation of alkyne. Among many possible

reagents, DMF-DMA (DMA- N,N-dimethylacetamide)

has been chosen. Applying gentle reactions conditions

proposed by Kim and co-workers [22] afforded aldehyde

6 in 11% yield. Adding higher amount of DMF led

to improvement of yield of compound 6 to 19%.

Subsequently, different procedure was used with alkyl-

lithium compounds as generators of acetylenic anions,

and DMF as formylating agent. The use of non-typical

hydrolysis consisting of addition of reaction mixture into

biphasic emulsion of MTBE (t-butyl-methyl ether) and

phosphorane buffer at 5°C (reverse quenching method)

J. Porphyrins Phthalocyanines 2014; 18: 2–16

SOLUBLE MESO-TETRAKIS(ARYLETHYNYL)PORPHYRINS

3

Br

CHO

OR

Br

PPh_3,CBr₄

CH₂Cl₂, 0 °C

C₁₀H₂₁

O

OC₁₀H₂₁

H₂₅C₁₂

O

OC₁₂H₂₅

RO

OR

RO

OR

4a

3a

3a R = C₁₂H₂₅

3b R = C_{10 21}

3c R = (CH₂CH₂O)₃CH₃

5a R = C₁₂H₂₅(96%)

H

5b R = C₁₀H₂₁(86%)

Method A:

1. DMF, DMF-DMA

2. HCl

Method B:

5c R = (CH₂CH₂O)₃CH₃(67%)

1. n-BuLi, DMF, THF

2. DMF, -35/-40 °C

InCl₃, 94%

3. KH₂PO₄, MTBE, 5 °C

19%

1. x equiv. BuLi

THF, -78 °C, t

2. NH₄Cl_aq

65%

.

CHO

OC₁₀H₂₁

C₁₀H₂₁

O

+

H₂₅C₁₂

O

OC₁₂H₂₅

RO

OR

NH HN

OC₁₂H₂₅

OR

7

6

4a R = C₁₂H₂₅(74%), t = 1 h, x = 7

4b R = C₁₀H₂₁(91%), 20 h, x = 10

4c R = (CH₂CH₂O)₃CH₃(12%), 22 h, x = 10

1. BF₃Et₂O, CH₂Cl₂

2. DDQ

3. Et₃N

Scheme 2.

OC₁₀H₂₁

C₁₀H₂₁

O

[23] allowed us to transform alkyne 4a into aldehyde 6

in 65% (Scheme 3). In order to increase conversion and

improve the yield of 6, various modiﬁcations have been

subsequently attempted (such as replacement of n-BuLi

with t-BuLi, varying reaction time, temperature as well

as substrate ratio) but all in vain.

OC₁₂H₂₅

C₁₂H₂₅

O

NH

N

C₁₂H₂₅

O

HN

C₁₂H₂₅

O

Having both substrates in hand, we carried out the

reaction of aldehyde 6 with dipyrrane 7 in toluene with

BF₃·Et₂O [13a] as catalyst (Scheme 3). Unfortunately, only

traces of the expected product were detected by (ESI-MS),

which could not be isolated. Reaction of 6 with 7 under

other reaction conditions such as TFA/CH₂Cl₂[24] and

BF₃·Et₂O/MeCN/NH₄Cl [24] also failed. Consequently, we

have changed the strategy. Unsubstituted dipyrrane 8 [25]

was reacted with aldehyde 3b into trans-A₂-porphyrin 9

(Scheme 4). In the next step smooth bromination afforded

dibromoporphyrin 10 [8c].

C₁₀H₂₁

O

OC₁₀H₂₁

11b

Scheme 3.

Compounds 11a and 11b were prepared via

Sonogashira coupling of porphyrin 10 with alkynes 4b

and 4a (Scheme 4). One has to emphasize that puriﬁca-

tion of these porphyrins was more troublesome than

typically, since non-porphyrin impurities possessed

almost the same R_f. Since SEC column also did not helped

to purify these products, we ﬁnally decided to utilize

magnesium insertion (which is known to drastically

change the polarity of porphyrin). Insertion of magnesium

[26] followed by straightforward puriﬁcation and removal

of magnesium (TFA, CHCl₃, RT), led to compounds 11a

and 11b in 31% and 34% respectively after three steps.

Dibromoporphyrin 10 was also subjected to Sonogashira

reaction with alkyne 4c possessing tetraethylene glycol

chains. In this case porphyrin 11c was isolated in 27%

yield after straightforward puriﬁcation. This was possible

due to different character of tetraethylene glycol chains

vs. decyl and dodecyl substituents. Higher polarity of

porphyrin 11c imparted by the presence of multiple

CH₂CH₂O groups resulted in differentiating of its R_fvs.

non-porphyrin impurities.

The strategy towards trans-A₂B₂-tetrakis(arylethynyl)

porphyrins, implied the synthesis of compound 13,

which is a perfect substrate for the Sonogashira reaction

leading to required products (Schemes 5 and 6). Direct

bromination of porphyrin 12 [10e] at two free meso-

positions with NBS was unsuccessful due to the formation

of more than ﬁve products which could not be separated.

J. Porphyrins Phthalocyanines 2014; 18: 3–16

4

A. NOWAK-KRÓL ET AL.

OC₁₀H₂₁

C₁₀H₂₁

O

1. TFA, CH₂Cl₂

2. DDQ

CHO

NH

N

3. Et₃N

+

NH HN

50%

C₁₀H₂₁

O

OC₁₀H₂₁

HN

OC₁₀H₂₁

8

3b

C₁₀H₂₁

O

OC₁₀H₂₁

9

NBS, CH₂Cl₂

MeOH, 3 h

99%

OR

OC₁₀H₂₁

C₁₀H₂₁

O

C₁₀H₂₁O

4a R = C₁₂H₂₅

OR

4b R = C_{10 21}

H

4c R = (CH₂CH₂O)₃CH₃

OR

RO

Pd₂(dba)₃, AsPh₃, Et₃N

toluene, THF

NH

N

NH

N

OR

Br

HN

RO

C₁₀H₂₁

O

OC₁₀H₂₁

C₁₀H₂₁

O

OC₁₀H₂₁

11a R = C₁₀H₂₁(31% after three steps)

11b R = C₁₂H₂₅(34% after three steps)

11c R = (CH₂CH₂O)₃CH₃(27%)

10

1. TFA, CHCl₃

MgI₂, DIPEA, CH₂Cl₂

2. Et₃N

OC₁₀H₂₁

C₁₀H₂₁

O

OC₁₀H₂₁

OR

RO

N

Mg

OR

RO

C₁₀H₂₁

O

OC₁₀H₂₁

Mg-11a R = C₁₀H₂₁

Mg-11b R = C₁₂H₂₅

Scheme 4.

J. Porphyrins Phthalocyanines 2014; 18: 4–16

SOLUBLE MESO-TETRAKIS(ARYLETHYNYL)PORPHYRINS

5

TIPS

CHO

+

NH HN

8

1. BF₃•Et₂O, CH₂Cl₂

2. DDQ

29%

NH

N

MgI₂, DIPEA, CH₂Cl₂

TIPS

Mg

TIPS

97%

HN

Mg-12

12

NBS, pyridine

CHCl₃

NBS, pyridine

CHCl₃

65%

Br

1. TFA, CHCl₃

2. Et₃N

NH

N

TIPS

Mg

Br

TIPS

94%

HN

N

Br

13

Mg-13

OC₁₀H₂₁

C₁₀H₂₁

O

OC₁₀H₂₁

4b

Pd₂(dba)₃, AsPh₃, Et₃N

toluene, THF, rt, 28 h

N

TIPS

Mg

TIPS

20%

C₁₀H₂₁

O

OC₁₀H₂₁

Mg-14

Scheme 5.

Consequently, we performed bromination on magnesium

complex Mg-12, leading to Mg-complex 5,15-dibromo-

10,20-bis[(triisopropylsilyl)ethynyl]porphyrin (Mg-13)

[10b]. Removal of Mg²⁺led smoothly to free base 13.

This porphyrin was subsequently transformed via

Sonogashira reaction with acetylene 4b into porphyrin

14 in 32% yield (Scheme 6). Prolongation of the reaction

time led to increase in the yield of trans-A₂B₂-porphyrin

14 to 86%. Analogous reaction with complex Mg-13,

afforded Mg-14 in 20% yield only (Scheme 5).

In the next step, silyl groups have been removed

using TBAF [27], and porphyrin 15 was subjected to

Sonogashira reaction with selected bromoarenes 16–17.

Meso-tetrakis(arylethynyl)porphyrin 18 was formed in

81% yields, however bromoarene 17 failed to react with

porphyrin 15.

J. Porphyrins Phthalocyanines 2014; 18: 5–16

6

A. NOWAK-KRÓL ET AL.

OC₁₀H₂₁

C₁₀H₂₁

O

OC₁₀H₂₁

4b

Pd₂(dba)₃, AsPh₃, Et₃N

toluene, THF, rt, t

NH

N

TIPS

13

TIPS

86%

HN

C₁₀H₂₁

O

OC₁₀H₂₁

14

86%

TBAF, THF

OC₁₀H₂₁

C₁₀H₂₁

O

C₁₀H₂₁O

16 R = CF₃, X = I

17 R = NPh₂, X = Br

R

X

Pd₂(dba)₃, AsPh₃, Et₃N

toluene, THF

NH

N

NH

N

R

HN

C₁₀H₂₁

O

OC₁₀H₂₁

C₁₀H₂₁

O

OC₁₀H₂₁

18 R = CF₃(81%)

19 R = NPh₂(traces)

15

Scheme 6.

Needless to say, the presence of four arylethynyl

through bis(arylethynyl)porphyrins 11a–11b to meso-

tetrakis(arylethynyl)porphyrins 14 and 18 (Fig. 1). Most

of free-base trans-A₂B₂-bis(arylethynyl)porphyrins

described so far possess absorption maxima around

445–460 nm for Soret band and 700 nm for Q-band

[8b,c, 13a, 28–30]. The exact l_maxis rather insensitive

to the electronic nature of substituents at arylethynyl

moieties. Both electron-withdrawing substituents and

electron-donating substituents have negligible effect on

linear absoprtion properties [8b, 28, 29]. The red shift

of absorption between trans-A₂B₂-bis(arylethynyl)

porphyrins and meso-tetrakis(arylethynyl)porphyrins

is ~20 nm on the Soret band and ~40 nm on the lowest

substituents at the periphery of porphyrin led to drop

in solubility of porphyrin 18 vs. porphyrins 11a and

15. While porphyrins 11a and 15 (possessing two

arylethynyl substituents) were soluble in CH₂Cl₂, CHCl₃,

toluene, EtOAc and acetone on the level >50 mg/1 mL,

the solubility of compound 18 was ~5 mg/1 mL (in

CH₂Cl₂, CHCl₃, and toluene) and ~1 mg/mL in EtOAc

and acetone.

Optical studies were performed in CH₂Cl₂and in CCl₄

(forporphyrin18duetotheplannedtwo-photonabsorption

studies). Both Soret band and Q-bands undergo signiﬁcant

red-shift while moving from 5,15-diarylporphyrin 9

J. Porphyrins Phthalocyanines 2014; 18: 6–16

SOLUBLE MESO-TETRAKIS(ARYLETHYNYL)PORPHYRINS

7

Fig. 1. Absorption spectra of porphyrins 11a (solid line), 15

(dashed line), 18 (dotted line) in CH₂Cl₂

Fig. 2. Absorption (dotted line) and emission (solid line)

spectra of porphyrin 18 in air saturated toluene. Porphyrin was

excited at 630 nm

Table 1. Linear optical properties of porphyrins 9, 11a,

11b, Mg-14, 14 and 18

Porphyrin

l

_Soret, nm

e, 10³cm^-1.M^-1

l_Q, nm

9^a

412

451

452

480

468

472

286

403

280

562

317

273

635

696

Table 2. Selected singlet and triplet data of porphyrin 18 in

toluene

11a^b

11b^b

Mg-14^b

14^b

Porphyrin

l_ﬂ, nm

T_s, ns

T, T_{n max}

t_T, ms

445

705

692

18

746

7.1

505

5

730

18^a

640, 736

Matsuo and co-workers (710 nm) [10b]. The Q-band

pattern of 18 is markedly different than that of H₂TPP.

The bands are broadened, red-shifted and the peak

extinction is enhanced by nearly one order of magnitude.

Bathochromic shift of absorptio n is also reﬂected

in red-shift of emission (Fig. 2). The ﬂuorescence of

porphyrin 18 has its maximum at 746 nm, while trans-

A₂B₂-bis(arylethynyl)porphyrins have emission typically

around 700 nm [28].

^ain CCl₄; ^bin CH₂Cl₂.

energy Q-band (Table 1). At the same time the Soret band

undergoes signiﬁcant broadening. Only slightly smaller

effect is visible if only two unsubstituted C–C triple

bonds are present at positions 10 and 20 (15, Fig. 1).

Porphyrin 18 displays Q-band absorption centered at

736 nm, which is more bathochromically shifted than

in the case of 5,15-bis[(4′-nitrophenyl)ethynyl]-10,20-

bis[(triisopropylsilyl)ethynyl]porphyrin described by

Detailed triplet studies were performed for porphyrin

18(Table2,Fig.3)usingnanosecondlaserﬂashphotolysis.

Deoxygenated samples in toluene were excited at 355 nm

Fig. 3. Triplet absorption of porphyrin 18 in deoxygenated toluene. Porphyrin was excited at 355 nm

J. Porphyrins Phthalocyanines 2014; 18: 7–16

8

A. NOWAK-KRÓL ET AL.

Table 3. Calculated energy levels and molecular orbitals for transitions for porphyrin Mg-11a

State

Energy, eV

f^a

m_x^b

m_y^b

H → L^d

H → L + 1

H-1 → L

H-1 → L + 1

1

2

3

4

1.96

2.1

0.65

-9.34

0.01

14.6

0.22

0.04

0.34

0.890049

0

0.430939

0.0009

2.42

0

-0.69304

0

0.706272

0

3.0

-0.14

12.1

-0.43561

0

0.876515

0

3.01

1.68

0.718717

0.699442

LUMO

HOMO-1

HOMO

LUMO + 1

b

c

d

^aCalculated oscillator strength. Transition dipole x component(D). Transition dipole y component(D). HOMO and LUMO CI

mixing coefﬁcient.

Fig. 4. Dependence of the 2PA cross-section of porphyrin 18 on laser wavelength in CCl₄solution

and the T₁-T_nabsorption was probed using a xenon white

light source. Lifetimes wereobtained by ﬁtting to a single

exponential decay. The results show that l_max(T₁-T_n)

absorption occurs at 505 nm and that t_T~ 450 ms, which

is ~4 times longer than that for two previously studied

trans-A₂B₂-bis(arylethynyl)porphyrins [8b]. One has

to note that corresponding values for H₂TPP are in the

range 220–1500 ms depending on the solvent [31] while

tetrakis(diphenylaminophenyl)porphyrin in toluene

decay with t_T~ 200 ms [31]. Previously we found that

the presence of two 4-cyanophenylethynyl substituents

at meso-positions of porphyrins enhances two-photon

absorption cross-section (s₂) from ~10 GM to 100 GM

at 840 nm excitation wavelength [29]. In this context

it seemed valuable to perform the study of two-photon

absorption for porphyrin 18, possessing analogous

electron-withdrawing groups (CF₃) but different

architecture. Due to the larger bathocromic shift of the

J. Porphyrins Phthalocyanines 2014; 18: 8–16

SOLUBLE MESO-TETRAKIS(ARYLETHYNYL)PORPHYRINS

9

Table 4. Calculated energy levels and molecular orbitals for transitions for porphyrin 18

State

Energy, eV

f^a

m_x^b

m_y^c

H → L^d

H → L + 1

H-1 → L

H-1 → L + 1

1

2

3

4

1.83

1.91

2.76

2.92

0.23

0.65

2.49

1.95

1.54

-7.94

11.4

5.50

5.24

0.369958

0.823864

0

0.750438

-0.34894

0.531094

0

-0.49076

0.220575

0.827315

0

0.184583

-0.34894

0

10.4

-9.63

9.14

-0.41469

0.895819

LUMO - 1

HOMO-1

HOMO

LUMO

b

c

d

^aCalculated oscillator strength. Transition dipole x component(D). Transition dipole y component(D). HOMO and LUMO CI

mixing coefﬁcient.

lowest energy Q-band the quadratic power dependence

of ﬂuorescence intensity was observed above 950 nm

where maximum 2PA cross-section is, s₂~500 GM

(Fig. 4).

y polarized, while states 2-4 have almost equal x and y

polarization.

Comparison of the 2PA spectra with previously

reported data shows that end-capping with the CF₃group

combined with the presence of two electron-donating

3,4,5-trialkoxyphenylethynyl substituents amplify the

maximum 2PA cross-section with respect to both neutral

bis(arylethynyl)porphyrins and bis(4′-cyanophenylethy-

nyl)porphyrins [29]. Finally DFT calculations were

performed to elucidate the origin of transitions for two

the most representative compounds i.e. Mg-11a and

18. The calculation results, show that both Q and Soret

bands originate from the combination of transitions

from HOMO-1, HOMO to LUMO and LUMO+1

levels (Tables 3 and 4). Although the overall molecule

has low symmetry, Mg-11a has a porphyrin core

with D_4hsymmetry and the optical transitions can be

analyzed assuming the entire molecule approximates

this symmetry. States 1 and 3 are polarized along the

phenylethynyl-porphyrin-phenylethynyl(x) axis while

states 2 and 4 are nearly degenerate with states 1 and 3

and are polarized along the phenyl-porphyrin-phenyl(y)

axis. The HOMO has signiﬁcant contribution from the

phenylethynyl ligand p orbitals and as a result states 1

and 3 have x polarization due to the HOMO→LUMO

contribution. Compound 18 is a free base porphyrin

having a core with D_2hsymmetry. All the states are

mixtures of transitions between the HOMO-1, HOMO

and LUMO, LUMO+1 MOs. State 1 is predominately

EXPERIMENTAL

General

All chemicals were used as received unless otherwise

noted. Reagent grade solvents (CH₂Cl₂, hexanes) were

distilled prior to use. All reported ¹H NMR spectra were

collected using a 200 MHz, 400 MHz, 500 MHz or

600 MHz spectrometer. Chemical shifts (d ppm) were

determined with TMS as the internal reference; J values

were given in Hz. Due to the presence of long alkyl

chains, in ¹³C NMR spectra of many compounds the

signals of carbon atoms overlap very strongly and it is

impossible to assign the number of signals corresponding

to actual number of magnetically non-identical protons.

The UV-vis absorption spectra were recorded in CH₂Cl₂

and CCl₄. The absorption wavelengths were reported in

nm with the extinction coefﬁcient in M^-1cm^-1in brackets.

The purge gas was high purity argon. Chromatography

was performed on silica (200–400 mesh) or alumina.

Preparative scale size exclusion chromatography (SEC)

was carried out using BioRad Bio-Beads S-X1 with

toluene or THF as an eluent. Dry column vacuum

chromatography (DCVC) was performed on Silicagel

type D 5F. The mass spectra were obtained by ﬁeld

desorption MS (FD-MS) or by electrospray MS

(ESI-MS). Diethyl (1-diazo-2-oxopropyl)phosphonate

J. Porphyrins Phthalocyanines 2014; 18: 9–16

10

A. NOWAK-KRÓL ET AL.

(2) was obtained according to literature procedure [12].

5-[3,4,5-tris(decyloxy)phenyl]dipyrrane (7) was obtained

according to literature procedure [13].

hexanes/CH₂Cl₂3:1) was performed to yield pure

product 4a (125 mg, 74%), which was crystallized from

hexanes; mp 44.5–45.4°C. ¹H NMR (400 MHz, CDCl₃):

d, ppm 0.88 (t, J = 6.8 Hz, 9H, CH₃), 1.18–1.38 (m, 48H,

CH₂), 1.40–1.51 (m, 6H, OCH₂CH₂CH₂), 1.66–1.86 (m,

6H, OCH₂CH₂), 2.99 (s, 1H, CH_alkyne), 3.91–3.99 (m, 6H,

OCH₂), 6.69 (s, 2H, ArH). ¹³C NMR (100 MHz, CDCl₃):

d, ppm 14.1, 22.7, 26.0, 26.1, 29.3, 29.36, 29.38, 29.57,

29.62, 29.65, 29.68, 29.73, 30.3, 31.91, 31.93, 69.1, 73.5,

75.7, 84.0, 110.6, 116.3, 139.4, 152.9. HR MS (ESI):

m/z calcd. for C₄₄H₇₈O₃Na [M + Na]⁺677.5849, found

677.5848.

Synthesis

5-(2,2-Dibromovinyl)-1,2,3-tris(dodecyloxy)ben-

zene (5a). CBr₄(755 mg, 2.3 mmol) was placed in

a round-bottomed ﬂask purged with argon and then

dissolved in anhydrous CH₂Cl₂(6 mL). The reaction

mixture was cooled to 0°C and PPh₃(1.185 g, 4.5 mmol)

was added. The mixture turned orange. In another round-

bottomed ﬂask purged with argon, aldehyde 3a (1.0 g,

1.5 mmol) was dissolved in anhydrous CH₂Cl₂(3 mL).

After 15 min (after PPh₃was added to CBr₄solution) the

solution of aldehyde 3a was added dropwise to the ﬂask

containing the generated ylide. After 5 min the solvent

was evaporated and the crude product was puriﬁed by

column chromatography (silica, hexanes/CH₂Cl₂3:2) to

obtain pure oleﬁn 5a (1.192 g, 96%) as a colorless solid,

which was crystallized (hexanes/EtOH) for analyses;

5-(2,2-Dibromovinyl)-1,2,3-tris(decyloxy)benzene

(5b). CBr₄(1.133 g, 3.4 mmol) was placed in a round-

bottomed ﬂask purged with argon. Then, it was dissolved

in anhydrous CH₂Cl₂(9 mL). The reaction mixture was

cooled to 0°C and PPh₃(1.778 g, 6.8 mmol) was added.

The mixture turned orange. In the second round-bottomed

ﬂask purged with argon aldehyde 3b (1.293 g, 2.25 mmol)

was dissolved in anhydrous CH₂Cl₂(9 mL). After 15 min

(after PPh₃was added to CBr₄solution), the solution of

aldehyde 3b was added dropwise to the ﬂask containing

the generated ylide. After 20 min the solvent was

evaporated and the crude product was puriﬁed by column

chromatography (silica_,hexanes to hexanes/CH₂Cl₂7:3)

to obtain pure oleﬁn 5b (1.408 g, 86%) as an colorless

product. ¹H NMR (500 MHz, CDCl₃): d, ppm 0.88 (t, J =

6.9 Hz, 9H, CH₃), 1.20–1.39 (m, 36H, CH₂), 1.41–1.50

(m, 6H, OCH₂CH₂CH₂), 1.70–1.84 (m, 6H, OCH₂CH₂),

3.94–3.99 (m, 6H, OCH₂), 6.76 (s, 2H, ArH), 7.37 (s,

1H, CH_vinyl). ¹³C NMR (125 MHz, CDCl₃): d, ppm 14.1,

22.67, 22.69, 26.1, 29.33, 29.38, 29.39, 29.57, 29.62,

29.66, 29.72, 30.3, 31.90, 31.93, 69.2, 73.4, 88.0, 107.2,

130.0, 136.8, 138.7, 152.8. HR MS (ESI): m/z calcd.

for C₃₈H₆₇Br₂O₃[M + H]⁺729.3452, found 729.3430.

Elemental analysis calcd. (%) C₃₈H₆₆Br₂O₃: C, 62.46; H,

9.10; Br, 21.87, found C, 62.52; H, 9.18; Br, 21.84.

1,2,3-Tris(decyloxy)-5-ethynylbenzene (4b). Alkene

5b (1.376 g, 1.88 mmol) was placed in a round-bottomed

ﬂask purged with argon and anhydrous THF (25 mL) was

added. The substrate was dissolved and the solution was

cooled to -78°C. Then, BuLi (2.5 M in hexane, 7.5 mL,

18.8 mmol) was added, the reaction mixture was stirred

at -78°C for 20 h and saturated NH₄Cl (60 mL) was

added. The layers were separated and the water layer

was extracted with EtOAc. The combined organic

extracts were dried (Na₂SO₄), ﬁltered and the solvent was

evaporated to obtain an oil which slowly solidiﬁed. The

crude product was puriﬁed by column chromatography

(silica, hexanes/CH₂Cl₂7:3) to obtain pure alkyne 4b

(973 mg, 91%) as a colorless solid. ¹H NMR (400 MHz,

CDCl₃): d, ppm 0.88 (t, J = 6.8 Hz, 9H, CH₃), 1.22–1.40

(m, 36H, CH₂), 1.40–1.50 (m, 6H, OCH₂CH₂CH₂), 1.67–

1.75 (m, 2H, OCH₂CH₂), 1.76–1.83 (m, 4H, OCH₂CH₂),

2.99 (s, 1H, CH_alkyne), 3.94 (t, J = 6.4 Hz, 6H, OCH₂), 6.69

(s, 2H, ArH). HR MS (ESI): m/z calcd. for C₃₈H₆₇O₃[M +

H]⁺571.5090, found 571.5096.

1

mp 35.3–36.6°C. H NMR (500 MHz, CDCl₃): d, ppm

0.88 (t, J = 7.0 Hz, 9H, CH₃), 1.24–1.37 (m, 48H, CH₂),

1.41–1.51 (m, 6H, OCH₂CH₂CH₂), 1.69–1.83 (m, 6H,

OCH₂CH₂), 3.93–3.99 (m, 6H, OCH₂), 6.76 (s, 2H, ArH),

7.37 (s, 1H, CH_vinyl). ¹³C NMR (125 MHz, CDCl₃): d, ppm

14.1, 22.7, 26.1, 29.36, 29.39, 29.41, 29.59, 29.63, 29.66,

29.69, 29.72, 29.74, 29.75, 30.3, 31.93, 31.94, 69.3, 73.4,

88.0, 107.3, 130.0, 136.8, 138.8, 152.9. HR MS (FD):

m/z calcd. for C₄₄H₇₈Br₂O₃812.4318, found 812.4331,

isotope proﬁles match. Anal. calcd. (%) C₄₄H₇₈Br₂O₃: C,

64.85; H, 9.65; Br, 19.61, found C, 64.67; H, 9.54; Br,

19.58.

1,2,3-Tris(dodecyloxy)-5-ethynylbenzene

(4a).

Method A. Diethyl 1-diazo-2-oxopropylphosphonate

(198 mg, 0.9 mmol) was added to a solution of aldehyde

3a (500 mg, 0.75 mmol) and Cs₂CO₃(489 mg, 1.5 mmol)

in i-PrOH (10 mL) and stirring was continued for 8 h. The

reaction mixture was diluted with Et₂O (20 mL), washed

with NaHCO₃(aq., 5%, 10 mL) and dried over Na₂SO₄.

After ﬁltration and evaporation of the solvent, the residue

was puriﬁed by two column chromatographies (silica,

hexanes/CH₂Cl₂4:1) to yield pure product 4a (96 mg,

19%), which was crystallized from hexanes. Method B.

Alkene 5a (209 mg, 0.26 mmol) was placed in a round-

bottomed ﬂask purged with argon and anhydrous THF

(3.5 mL) was added. The substrate was dissolved and

the solution was cooled to -78°C. Then, BuLi (2.5 M

in hexane, 0.73 mL, 1.83 mmol) was added and the

mixture turned orange. The reaction mixture was stirred

at -78°C for 1 h. Afterwards, saturated NH₄Cl (6 mL)

was added. The layers were separated and the organic

layer was washed with water, dried (Na₂SO₄), ﬁltered and

the solvent was evaporated to obtain an orange oil. The

initial puriﬁcation by column chromatography (silica,

hexanes/CH₂Cl₂4:1) afforded a mixture of the substrate

and product 4a. The consecutive chromatography (silica,

J. Porphyrins Phthalocyanines 2014; 18: 10–16

SOLUBLE MESO-TETRAKIS(ARYLETHYNYL)PORPHYRINS

11

5-(2,2-Dibromovinyl)-1,2,3-tris(2-(2-(2-methok-

syethoxy)ethoxy)ethoxy)benzene (5c). CBr₄(0.910 g,

2.74 mmol) was placed in a round-bottomed ﬂask purged

with argon. Then, it was dissolved in anhydrous CH₂Cl₂

(7.5 mL). The reaction mixture was cooled to 0°C, PPh₃

(1.430 g, 5.45 mmol) was added and the mixture turned

orange. In another round-bottomed ﬂask purged with

argon aldehyde 3c (1.071 g, 1.81 mmol) was dissolved

in anhydrous CH₂Cl₂(7.5 mL). After 15 min (after PPh₃

was added to CBr₄solution), the solution of aldehyde 3c

was added dropwise to the ﬂask containing the generated

ylide. After 20 min the solvent was evaporated and the

crude product was puriﬁed by column chromatography

(silica_,EtOAc then EtOAc/5% MeOH). The consecutive

chromatography (silica_,EtOAc then EtOAc/MeOH

9:1) afforded to obtain pure oleﬁn 5c (912 mg, 67%)

CH₂Cl₂4:1 to 1:1) to collect the substrates and pure

product 6 (12 mg, 19%). H NMR (400 MHz, CDCl₃):

1

d, ppm 0.88 (t, J = 6.8 Hz, 9H, CH₃), 1.21–1.40 (m, 48H,

CH₂), 1.41–1.52 (m, 6H OCH₂CH₂CH₂), 1.68–1.77 (m,

2H, OCH₂CH₂), 1.78–1.86 (m, 4H, OCH₂CH₂), 3.96

(t, J = 6.8 Hz, OCH₂), 4.01 (t, J = 6.4 Hz, OCH₂), 6.81

(s, 2H, ArH), 9.39 (s, 1H, CHO). ¹³C NMR (100 MHz,

CDCl₃): d, ppm 14.1, 22.7, 26.0, 29.20, 29.36, 29.38,

29.54, 29.61, 29.65, 29.68, 29.71, 30.3, 31.9, 69.2,

73.7, 88.0, 96.5, 111.8, 113.3, 141.8, 153.1, 176.6. HR

MS (ESI): m/z calcd. for C₄₅H₇₉O₄[M + H]⁺683.5978,

found 683.5984. Method B. Alkyne 4a (60 mg, 0.09

mmol) was placed in a round-bottomed ﬂask and dried

under vacuum for 1 h. Then, anhydrous THF (2.25 mL)

was added. The solution was cooled to -35°C and BuLi

(2.5Minhexane,0.36mL,0.9mmol)wasaddeddropwise.

Subsequently, DMF (0.14 mL, 1.8 mmol) was added to

the reaction mixture at -35–(-40)°C and the solution

was stirred for 45 min. Afterwards, the reaction mixture

was poured into the vigorously stirred bilayer mixture

of aqueous solution of KH₂PO₄(490 mg, 3.6 mmol)

and MTBE (2.7 mL). The layers were separated and

the organic layer was washed with water. The organic

extracts were dried (MgSO₄), ﬁltered and the solvent was

removed in vacuo. The crude product was puriﬁed by

column chromatography (silica, hexanes, then hexanes/

CH₂Cl₂4:1) to obtain pure aldehyde 6 (41 mg, 65%).

5,15-Bis[3,4,5-tris(decyloxy)phenyl]porphyrin (9).

Dipyrrane 8 (1.14 g, 7.8 mmol) and aldehyde 3b (4.46 g,

7.8 mmol) were dissolved in CH₂Cl₂(1 l). For 0.5 h

the solution was purged with argon and simultaneous

sonication was applied. Then, TFA (0.38 mL, 5.0 mmol)

was added and the reaction was stirred for 75 min. In

the second step, DDQ (2.25 g, 9.9 mmol) was added and

the mixture was stirred for 1 h. Afterwards, the reaction

mixture was ﬁltered through a plug of Al₂O₃(Al₂O₃,

CH₂Cl₂) and evaporated to dryness. The crude product

was chromatographed (silica, hexane/CH₂Cl₂4:1 to 1:1),

to obtain pure product 9 (2.69 g, 50%). Spectral and

physical properties concur with published data [8c].

5,15-Dibromo-10,20-bis[3,4,5-tris(decyloxy)phenyl]

porphyrin (10). To the solution of porphyrin 9 (100 mg,

0.071 mmol) in CH₂Cl₂(3.5 mL), MeOH (0.5 mL) and

NBS (38 mg, 0.21 mmol) were added and the reaction

was stirred at rt for 3 h. Then, the crude product was

evaporated and puriﬁed by column chromatography

(silica, hexanes/0.9% EtOAc) to obtain pure product 10

(110 mg, 99%). Spectral and physical properties concur

with published data [8c].

1

as a colorless oil. H NMR (400 MHz, CDCl₃): d, ppm

3.37 (s, 9H, CH₃), 3.48–3.57 (m, 6H, OCH₂), 3.59–3.68

(m, 6H, OCH₂), 3.69-3.74 (m, 6H, OCH₂), 3.78–3.81

(m, 6H, OCH₂), 3.82–3.88, (m, 6H, OCH₂), 4.11–4.21

(m, 6H, OCH₂), 6.80 (s, 2H, ArH), 7.35 (s, 1H, H_vinyl).

¹³C NMR (100 MHz, CDCl₃): d, ppm 29.7, 59.0, 68.9,

69.6, 70.48, 70.53, 70.64, 70.77, 71.9, 72.3, 84.7, 88.7,

108.3, 130.3, 136.4, 152.3. HR MS (ESI): m/z calcd. for

C₂₉H₄₈Br₂O₁₂Na [M + Na]⁺769.1405, found 769.1428.

5-Ethynyl-1,2,3-tris(2-(2-(2-methoxyethoxy)ethoxy)

ethoxy)benzene (4c). Oleﬁn 5c (724 mg, 0.97 mmol) was

placed in a round-bottomed ﬂask purged with argon and

anhydrous THF (13 mL) was added. The substrate was

dissolved and the solution was cooled to -78°C. Then,

BuLi (2.5 M in hexane, 3.9 mL, 9.8 mmol) was added

and the reaction mixture was stirred at -78°C for 22 h.

Afterwards, saturated NH₄Cl (30 mL) was added. The

layers were separated and the water layer was extracted

with EtOAc. The combined organic extracts were dried

(Na₂SO₄), ﬁltered and the solvent was evaporated. The

crude product was puriﬁed by column chromatography

(silica, EtOAc, then EtOAc/MeOH 19:1 to 9:1) to obtain

pure alkyne 4c (68 mg, 12%) as a colorless oil. ¹H NMR

(400 MHz, CDCl₃): d, ppm 3.36 (s, 9H, CH₃), 3.50–3.55

(m, 6H, OCH₂), 3.60–3.66 (m, 7H, H_alkyne, OCH₂), 3.69–

3.75 (m, 6H, OCH₂), 3.77 (t, J = 4.8 Hz, 6H, OCH₂), 3.83

(t, J = 5.2 Hz, 6H, OCH₂), 4.11–4.16 (m, 6H, OCH₂),

6.72 (s, 2H, ArH). ¹³C NMR (100 MHz, CDCl₃): d, ppm

59.0, 68.8, 69.6, 70.47, 70.51, 70.61, 70.64, 70.78, 71.9,

72.3, 76.2, 83.5, 111.7, 116.8, 139.7, 152.4. HR MS

(ESI): m/z calcd. for C₂₉H₄₈O₁₂Na [M + Na]⁺611.3038,

found 611.3055.

[3,4,5-Tris(dodecyloxy)phenyl]propynal (6).

Method A. To alkyne 4a (60 mg, 0.092 mmol), placed

in a sealed tube, DMF (135 ml) and DMF-DMA (25 ml,

0.188 mmol) were added. The solution was stirred at

80°C for 23 h. Later, the reaction mixture was poured

into HCl_aq(pH = 4; 20 mL) and extracted three times with

Et₂O. The organic extracts were dried (Na₂SO₄), ﬁltered

and the solvent was removed in vacuo. The crude product

was puriﬁed by column chromatography (silica, hexanes/

5,15-Bis[3,4,5-tris(decyloxy)phenyl]-10,20-bis

[(3,4,5-tris(decyloxy)phenyl)ethynylporphyrin (11a).

A dried Schlenk tube, purged with argon, was charged

with porphyrin 10 (100 mg, 0.064 mmol) and alkyne 4b

(220 mg, 0.39 mmol). The substrates were dissolved in

anhydrous toluene (10 mL) and anhydrous THF (3 mL).

Then, Et₂NH (3 mL, 21 mmol) was added, followed by

AsPh₃(64 mg, 0.21 mmol) and Pd₂(dba)₃·CHCl₃(36 mg,

J. Porphyrins Phthalocyanines 2014; 18: 11–16

12

A. NOWAK-KRÓL ET AL.

0.035 mmol). The reaction mixture was stirred at rt for

40 h. Next, the second portion of alkyne 4b (110 mg,

0.19mmol),Pd₂(dba)₃·CHCl₃(36mg,0.035mmol),AsPh₃

(64 mg, 0.21 mmol) as well as Et₃N (2 mL, 14 mmol)

were added. The reaction mixture was stirred additionally

at rt for 30 h. Afterwards, the reaction mixture was

ﬁltered through a short plug of celite and evaporated. The

crude product was chromatographed (silica, hexanes/

CH₂Cl₂7:3 to 7:13). The consecutive SEC (THF) did

not allow to remove a non-porphyrinogen ﬂuorescent

compound. Therefore, compound 11a was transformed

into magnesium complex. Porphyrin 11a was dissolved

in CH₂Cl₂(2.5 mL) and DIPEA (N,N-diisopropylethyl-

amine) (0.21 mL, 1.2 mmol) was added, followed by

MgI₂(905 mg, 3.3 mmol). After 2.5 h the solvent was

removed in vacuo and the crude product was puriﬁed by

column chromatography (silica, hexanes then hexanes/

CH₂Cl₂1:1, then CH₂Cl₂) to obtain pure complex

Mg-11a. Then, the complex was dissolved in CHCl₃

(2.1 mL) and TFA (11 μl, 0.14 mmol) was added. The

color of the mixture changed from green to brown. After

8 min Et₃N (34 ml, 0.24 mmol) was added. Then, the

crude product was evaporated and puriﬁed by column

chromatography (silica, hexanes, then hexanes/CH₂Cl₂

7:3 to 1:1) to obtain pure product 11a (50 mg, 31% after

three steps). UV-vis (CH₂Cl₂): l, nm (e) 451 (403 000),

523 (7 200), 608 (60 100), 696 (34 100), 805 (1 000). ¹H

NMR (500 MHz, CDCl₃): d, ppm -1.93 (br s, 2H; NH),

0.78–0.96 (m, 36H, CH₃), 1.15–1.61 (m, 164H, CH₂),

1.64–1.73 (m, 4H, OCH₂CH₂CH₂), 1.79–2.03 (m, 24H,

OCH₂CH₂), 4.07–4.14 (m, 12H, OCH₂), 4.17 (t, J = 6.5

Hz, 8H, OCH₂), 4.31 (t, J = 6.5 Hz, 4H; OCH₂), 7.21 (s,

4H, ArH), 7.40 (s, 4H, ArH), 8.93 (d, J = 4.6 Hz, 4H,

b-H), 9.65 (d, J = 4.6 Hz, 4H, b-H). ¹³C NMR (125 MHz,

CDCl₃): d, ppm 14.05, 14.09, 14.12, 14.14, 22.63, 22.67,

22.71, 22.74, 26.15, 26.16, 26.3, 29.31, 29.36, 29.42,

29.44, 29.45, 29.47, 29.51, 29.54, 29.61, 29.61, 29.64,

29.67, 29.70, 29.75, 29.77, 29.9, 30.4, 30.6, 31.86, 31.91,

31.96, 31.99, 69.4, 73.7, 73.8, 90.6, 97.8, 101.3, 110.3,

114.3, 118.2, 122.0, 136.3, 138.1, 139.7, 151.4, 153.4.

HR MS (FD): m/z calcd. for C₁₆₈H₂₇₀N₄O₁₂2536.0640,

found 2536.0601, isotope proﬁles match.

(1 mL) and DIPEA (0.9 mL, 1.2 mmol) was added,

followed by MgI₂(100 mg, 0.36 mmol). After 3.5 h the

solvents were removed in vacuo and the crude product

was puriﬁed by column chromatography (silica, hexanes/

CH₂Cl₂3:1 to 7:3) to obtain pure complex Mg-11b. Then,

the complex was dissolved in CHCl₃(0.9 mL) and TFA

(5 ml, 0.065 mmol) was added. After 10 min the reaction

was quenched with Et₃N (34 ml, 0.24 mmol). The solvents

were evaporated and the crude product was puriﬁed by

column chromatography (silica, hexanes/CH₂Cl₂7:3

to 1:1) to obtain pure product 11b (30 mg, 34% after

three steps). UV-vis (CH₂Cl₂): l, nm (e) 452 (280

1

000), 613 (42 300), 705 (22 900). H NMR (500 MHz,

CDCl₃): d, ppm -1.93 (br s, 2H; NH), 0.81–0.94 (m, 36H,

CH₃), 1.02–1.47 (m, 168H, CH₂), 1.47–1.62 (m, 20H,

OCH₂CH₂CH₂), 1.64–1.74 (m, 4H, OCH₂CH₂CH₂),

1.76–2.08 (m, 24H, OCH₂CH₂), 4.08–4.15 (m, 12H,

OCH₂), 4.18 (t, J = 6.5 Hz, 8H, OCH₂), 4.31 (t, J = 6.5 Hz,

4H; OCH₂), 7.21 (s, 4H, ArH), 7.41 (s, 4H, ArH), 8.94 (d,

J = 4.6 Hz, 4H, b-H), 9.66 (d, J = 4.6 Hz, 4H, b-H). HR

MS (FD): m/z calcd. for C₁₈₀H₂₉₄N₄O₁₂2704.2518, found

2704.2473, isotope proﬁles match.

5,15-Bis[3,4,5-tris(decyloxy)phenyl]-10,20-bis

[(3,4,5-tris(2-(2-(2-methoxyethoxy)ethoxy)ethoxy)

phenyl)-ethynyl]porphyrin (11c). A dried Schlenk tube,

purged with argon, was charged with porphyrin 10 (31 mg,

0.020 mmol) and alkyne 4c (47 mg, 0.080 mmol). The

substrates were dissolved in anhydrous toluene (3.1mL)

and anhydrous THF (0.85 mL). Next, AsPh₃(32 mg,

0.10 mmol), Pd₂(dba)₃·CHCl₃(18 mg, 0.017 mmol)

and Et₃N (1.1 mL, 7.9 mmol) were added. The reaction

mixture was stirred at rt for 21.5 h. Then, the second

portion of Pd₂(dba)₃·CHCl₃(18 mg, 0.017 mmol) was

added. The reaction mixture was stirred at rt for 2 d.

Later, the reaction mixture was ﬁltered through a short

plug of celite and evaporated. The crude product was

chromatographed (silica, hexanes, then hexanes/EtOAc

4:1 to 1:4, then EtOAc, then EtOAc/2% MeOH to

EtOAc/5% MeOH). The consecutive chromatography

(silica, toluene/acetone 7:3) was performed to obtain

pure product 11c (14 mg, 27%) as a green solid. UV-vis

(CCl₄): l, nm (e) 450 (154 000), 521 (5 000), 606 (20

1

5,15-Bis[3,4,5-tris(decyloxy)phenyl]-10,20-bis

[(3,4,5-tris(dodecyloxy)phenyl)ethynyl]porphyrin

(11b). A dried Schlenk tube, purged with argon, was

charged with porphyrin 10 (50 mg, 0.032 mmol) and

alkyne 4a (65 mg, 0.099 mmol). The substrates were

dissolved in anhydrous toluene (10 mL) and anhydrous

THF (10 mL). Then, AsPh₃(20 mg, 0.065 mmol) and

Pd₂(dba)₃·CHCl₃(18 mg, 0.017 mmol) were added. The

reaction mixture was stirred at rt for 18 h. Afterwards,

the reaction mixture was ﬁltered through a short

plug of celite and evaporated. The crude product was

chromatographed (SEC, toluene, then SEC, THF). The

consecutive DCVC was performed (silica, hexanes/

CH₂Cl₂3:2). Subsequently, porphyrin 11b, contaminated

with a ﬂuorescent compound, was dissolved in CH₂Cl₂

600), 697 (10 500). H NMR (500 MHz, CDCl₃): d,

ppm -1.95 (br s, 2H, NH); 0.78–0.96 (m, 18H, CH₃),

1.04–1.73 (m, 84H, CH₂), 1.85–1.92 (m, 8H, OCH₂CH₂),

1.94–2.03 (m, 4H, OCH₂CH₂), 3.35 (s, 12H, OCH₃), 3.39

(s, 6H, OCH₃), 3.51–3.57 (m, 8H, OCH₂), 3.57–3.61 (m,

4H, OCH₂), 3.64–3.70 (m, 12H, OCH₂), 3.64–3.76 (m,

12H, OCH₂), 3.76–3.85 (m, 12H, OCH₂), 3.87–3.93 (m,

4H, OCH₂), 3.95–4.02 (m, 8H, OCH₂), 4.12 (t, J = 6.5

Hz, 8H, OCH₂), 4.24–4.34 (m, 8H, OCH₂), 4.34–4.40 (m,

8H, OCH₂), 7.26 (overlapping with the signal of CHCl₃

s, 4H, ArH), 7.40 (s, 4H, ArH), 8.94 (d, J = 4.4 Hz, 4H,

b-H), 9.63 (d, J = 4.4 Hz, 4H, b-H). ¹³C NMR (125 MHz,

CDCl₃): d, ppm 14.06, 14.10, 14.14, 22.63, 22.68, 22.74,

26.2, 26.3, 29.3, 29.46, 29.47, 29.54, 29.6, 29.7, 29.8,

29.9, 30.6, 31.9, 32.0, 59.0, 69.2, 69.4, 69.8, 70.6, 70.8,

J. Porphyrins Phthalocyanines 2014; 18: 12–16

SOLUBLE MESO-TETRAKIS(ARYLETHYNYL)PORPHYRINS

13

70.9, 72.0, 72.6, 73.8, 91.0, 97.3, 101.0, 111.5, 114.2,

118.6, 122.0, 127.8, 136.2, 138.1, 151.4, 152.9. HR

MS (ESI): m/z calcd. for C₁₅₀H₂₃₄N₄O₃₀Na₂[M + 2Na]²⁺

1308.8346, found 1308.8376, isotope proﬁles match.

[5,15-Bis[[3,4,5-tris(decyloxy)phenyl]ethynyl]-

10,20-bis[(triizoprophylosilyl)ethynyl]-porphyrinato]

magnesium (Mg-14). A dried Schlenk tube, purged with

argon, was charged with porphyrin Mg-13 (100 mg, 0.12

mmol) and alkyne 4b (272 mg, 0.48 mmol). The substrates

were dissolved in anhydrous toluene (18 mL), anhydrous

THF (5 mL) and Et₃N (6.8 mL, 0.049 mol). The vessel

was evacuated and backﬁlled with argon (this process was

repeated three times). Then, AsPh₃(90 mg, 0.29 mmol)

and Pd₂(dba)₃(54 mg, 0.052 mmol) were added. The

reaction mixture was stirred at rt for 28 h. Afterwards, the

reaction mixture was ﬁltered through a short plug of celite

and evaporated. The crude product was chromatographed

(Al₂O₃, hexanes/EtOAc/Et₃N 98:1:1 to 97:2:1). The

consecutive chromatography (Al₂O₃, hexanes/CH₂Cl₂

1:1 to 9:16) afforded pure product Mg-14 (43 mg, 20%)

as a green solid. UV-vis (CH₂Cl₂): l, nm (e) 480 (562

5,15-Bis[[3,4,5-tris(decyloxy)phenyl]ethynyl]-

10,20-diethynylporphyrin (15). A dried Schlenk tube,

purged with argon, was charged with porphyrin 14

(190 mg, 0.105 mmol). The porphyrin was dissolved in

anhydrous THF (20 mL). Then, TBAF (1.0 M, 0.45 mL,

0.45 mmol) was added. The reaction was stirred at

rt in argon atmosphere for 40 min. The solution was

concentrated and the crude product was chromatographed

(silica, hexanes/CH₂Cl₂3:2) to obtain pure product 15

which was suspended in hexanes and centrifuged (135

mg, 86%) affording porphyrin 15 as a green solid.

UV-vis (CH₂Cl₂): l, nm (e) 467 (266 000), 537 (6 100),

578 (11 200), 625 (50 500), 721 (12 900). ¹H NMR (600

MHz, CDCl₃): d, ppm -2.57 (s, 2H, NH), 0.87–0.92 (2

overlapping t, 18H, CH₃), 1.29–1.48 (m, 72H, CH₂),

1.56–1.63 (m, 12H, OCH₂CH₂CH₂), 1.82–1.89 (m, 4H,

OCH₂CH₂), 1.92–1.99 (m, 8H, OCH₂CH₂), 4.10–4.14

(m, 4H, OCH₂), 4.15 (s, 2H, CH_alkyne), 4.20–4.24 (m, 8H,

OCH₂), 7.21 (s, 4H, ArH), 9.32–9.37 (m, 8H, b-H). ¹³C

NMR (150 MHz, CDCl₃): d, ppm 14.11, 14.13, 22.70,

22.73, 26.20, 26.22, 29.40, 29.44, 29.52, 29.65, 29.68,

29.73, 29.80, 30.5, 31.9, 32.0, 69.5, 73.8, 84.6, 84.8,

89.7, 98.2, 100.6, 102.5, 110.5, 118.0, 139.9, 153.4.

Anal. calcd. (%) for C₁₀₀H₁₄₂N₄O₆: C, 80.27; H, 9.57; N,

3.74, found C, 80.07; H, 9.61; N, 3.67.

5,15-bis[[3,4,5-tris(decyloxy)phenyl]ethynyl]-

10,20-bis[[4-(trifluoromethyl)phenyl]ethynyl]por-

phyrin (18). A dried Schlenk tube, purged with argon,

was charged with porphyrin 15 (40 mg, 0.027 mmol).

The porphyrin was dissolved in anhydrous THF (6 mL)

and 1-iodo-4-(triﬂuoromethyl)benzene (16; 31 ml, 0.21

mmol), followed by Et₃N (1.5 mL, 11 mmol), Pd₂dba₃

(18 mg, 0.017 mmol) and AsPh₃(30 mg, 0.098 mmol)

were added. The reaction mixture was stirred at rt for

26.5 h. Afterwards, the reaction mixture was ﬁltered

through a short plug of celite and evaporated. The crude

product was puriﬁed by SEC (THF). The consecutive

chromatography (silica, hexanes/CH₂Cl₂3:1) was

performed to obtain pure product 26 (39 mg, 81%) as a

green solid. UV-vis (CCl₄): l, nm (e) 472 (273 000), 640

(54 900), 736 (16 200). ¹H NMR (500 MHz, CDCl₃): d,

ppm -2.91 (s, 2H, NH), 0.82–0.96 (m, 18H, CH₃), 1.28–

1.50 (m, 72H, CH₂), 1.51–1.58 (m, 8H, OCH₂CH₂CH₂),

1.59–1.68 (m, 4H, OCH₂CH₂CH₂), 1.83–1.91 (m, 4H,

OCH₂CH₂), 1.92–2.01 (m, 8H, OCH₂CH₂), 4.09–4.15

(m, 4H, OCH₂), 4.16–4.24 (m, 8H, OCH₂), 7.12 (s, 4H,

ArH), 7.81 (br s, 4H, ArH), 8.02 (AA’BB’, J = 5.4 Hz,

2x2H,), 9.00–9.13 (m, 8H, b-H). ¹³C NMR (125 MHz,

CDCl₃): d, ppm 14.1, 22.7, 26.26, 26.30, 29.44, 29.48,

29.60, 29.70, 29.77, 29.85, 30.5, 32.0, 69.5, 73.8, 89.6,

93.5, 95.8, 98.4, 101.0, 102.6, 110.4, 117.9, 118.7, 122

(q, J = 251.4 Hz), 125.1, 125.6, 127.4, 130.2, 131.83,

140.0, 153.4. LR MS (FD): m/z calcd. for C₁₁₄H₁₄₈F₆N₄O₆

1783.1, found 1783.1; isotope proﬁles match.

1

000), 634 (20 100), 692 (80 800). H NMR (400 MHz,

CD₂Cl₂): d, ppm 0.78–0.83 (m, 24H, CH₃, CH), 1.00–1.40

(m, 72H, CH₂), 1.40–1.60 (m, 36H, CH₃), 1.48–1.55 (m,

12H, OCH₂CH₂CH₂), 2.50–2.95 (m, 12H, OCH₂CH₂),

3.65–3.95 (m, 6H, OCH₂), 6.83 (s, 4H, ArH), 9.56 (d, J =

4.0 Hz, 4H, b-H), 9.62 (d, J = 4.0 Hz, 4H, b-H).

5,15-Bis[[3,4,5-tris(decyloxy)phenyl]ethynyl]-10,

20-bis[(triizoprophylosilyl)ethynyl]porphyrin (14). A

dried Schlenk tube, purged with argon, was charged with

porphyrin 13 (204 mg, 0.25 mmol) and alkyne 4b (551 mg,

0.97 mmol). The substrates were dissolved in anhydrous

toluene (37 mL), anhydrous THF (10 mL) and Et₃N (14

mL, 0.1 mol). The vessel was evacuated and backﬁlled with

argon (this process was repeated three times). Then, AsPh₃

(150 mg, 0.49 mmol) and Pd₂(dba)₃(100 mg, 0.097 mmol)

were added. The reaction mixture was stirred at rt for

14.5 h. Later, the mixture was ﬁltered through a short plug

of celite and evaporated. The crude product was puriﬁed

twice by SEC (toluene). The consecutive chromatography

(silica, hexanes/CH₂Cl₂4:1 to 7:3) afforded pure product

14 (384 mg, 86%). UV-vis (CH₂Cl₂): l, nm (e) 468 (317

000), 588 (14 700), 635 (63 700), 730 (20 300). ¹H NMR

(500 MHz, CDCl₃): d, ppm -1.52 (s, 2H, NH), 0.87–0.92 (2

overlapping t, 18H, CH₃), 1.29–1.54 (m, 114H, SiCHCH₃,

CH₂, SiCH), 1.56–1.62 (m, 12H, OCH₂CH₂CH₂), 1.81–

1.88 (m, 4H, OCH₂CH₂), 1.90–1.98 (m, 8H, OCH₂CH₂),

4.12 (t, J = 6.6 Hz, 4H, OCH₂), 4.18–4.22 (m, 8H, OCH₂),

7.22 (s, 4H, ArH), 9.57–9.61 (m, 8H, b-H). ¹³C NMR

(125 MHz, CDCl₃): d, ppm 11.9, 14.11, 14.14, 19.1,

22.70, 22.73, 26.18, 26.20, 29.39, 29.44, 29.49, 29.51,

29.64, 29.66, 29.71, 29.73, 29.80, 30.4, 31.9, 32.0, 69.5,

73.7, 89.8, 98.3, 100.3, 102.7, 102.9, 107.8, 110.4, 118.0,

139.9, 153.4. HR MS (FD): m/z calcd. for C₁₁₈H₁₈₂N₄O₆Si₂

1807.3598, found 1807.3528, isotope proﬁles match. Anal.

calcd. (%) for C₁₁₈H₁₈₂N₄O₆Si₂: C, 78.35; H, 10.14; N,

3.10, found C, 78.38; H, 10.07; N, 3.28.

Two-photon absorption measurements were carried

out using a wavelength-tunable femtosecond laser system

that comprises a Ti:Sapphire femtosecond oscillator

J. Porphyrins Phthalocyanines 2014; 18: 13–16

14

A. NOWAK-KRÓL ET AL.

(Mira 900, Coherent Inc.) pumped by a CW frequency-

doubled Nd:YAG laser (Verdi, Coherent Inc.) and a 1-kHz

repetition rate Ti:Sapphire femtosecond regenerative

ampliﬁer (Legend H, Coherent Inc.). The pulses from the

Ti:sapphire ampliﬁer are down converted with an optical

parametric ampliﬁer, OPA (TOPAS-C, Quantronix),

whose output signal (idler) is continuously tunable from

1100 to 1600 (1600 to 2200) nm. The second harmonic

of meso-substituted A₂-porphyrins followed by bromi-

nation and two consecutive Sonogashira couplings. We

proved that the presence of polyalkoxyphenyl substi-

tuents ensures desirable physical parameters of such

p-extended porphyrins. Combining this property with

very good secondary properties (strong absorption of red

light — e~50000 and a long triplet state lifetime) makes

them good candidates for nonlinear optical materials.

Porphyrin possessing two aromatic electron-withdrawing

substituents and two aromatic electron-donating

substituents at trans-arrangement is more polarized than

in majority of other porphyrins, which is probably the

reason for a signiﬁcant increase of triplet state lifetime

and in two-photon absorption cross-section.

of idler was used for two-photon excitation in the l_ex

=

800–1100 nm region and the fundamental of signal in the

1100–1400 nm region. The OPA output signal pulse energy

was 100–250 mJ (5–10 mJ after frequency doubling), and

the pulse duration was 70–120 fs. Brieﬂy, the linearly

polarized excitation laser beam was slightly focused with

an f = 25-cm lens onto the sample solution contained in a

1 × 1 cm²spectroscopic cell and placed 15 cm behind the

lens. A small fraction of the beam was split off by a thin

glass plate placed just before the sample and directed to the

reference detector (Molectron). The sample ﬂuorescence

was collected with a spherical mirror (f = 50 cm, diameter

d = 10 cm) and focused with magniﬁcation ratio ~1 on

the entrance slit of an imaging grating spectrometer

(Jobin Yvon Triax 550). The 2PA spectrum (in relative

units) was obtained by tuning the wavelength of OPA,

and measuring the corresponding intensity of two-photon

excited ﬂuorescence. The wavelength tuning of OPA and

data collection were computer-controlled with a LabView

routine. At each wavelength, the ﬂuorescence intensity

was normalized to the square of the excitation photon

ﬂux, measured in the reference channel. The correction to

the spectral variations of the OPA output (pulse duration

and beam spatial proﬁle) was done by using Rhodamine B

in methanol as a standard, whose 2PA spectrum is well-

characterized. To exclude possible artifacts, e.g. due to

absorption at wavelengths close to the linear absorption,

we checked that at each wavelength the ﬂuorescence

signal increased as a square of the excitation intensity.

Absolute 2PA cross-sections were measured using relative

ﬂuorescence technique as described with Rhodamine B as

a standard. To obtain absolute 2PA spectra in GM units, all

relative 2PA spectra were calibrated to the known (at one

wavelength in each spectral region) absolute cross-section

value. Styryl 9M in CHCl₃was used as reference standard

[32]. The 2PA properties were measured in CCl₄solutions.

Calculations performed with Gaussian 09, Revision

C.01. Following ground state optimization(b3lyp/6-

31g(d)/PCM(CCl₄), TDDFT(cam-b3lyp/6-31g(d))/

PCM(CCl₄) calculations were carried out. The calculated

state energies, oscillator strengths, transition dipoles,

CI mixing coefﬁcients and molecular orbital images for

compounds Mg-11a and 18 are shown in Table 3 and 4.

Acknowledgements

We thank Polish National Centre for Research and

Development (grant OLAE+) and the Foundation for

Polish Science (Ventures-2009-4/6). A.R. acknowledges

support from AFOSR Grant FA9550-09-1-0219. The

authors thank A. Mikhailov for invaluable assistance in

2PA measurements.

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Article Doi

Soluble meso-tetrakis(arylethynyl)porphyrins - synthesis and optical properties

DOI: 10.1142/S1088424614500904

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Article abstract of DOI:10.1142/S1088424614500904

Full text of DOI:10.1142/S1088424614500904

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