Synthetic, structural, and spectroscopic studies of bis(porphyrinzinc) complexes linked by two-atom conjugating bridges

Article abstract of DOI:10.1002/ejoc.201500183

Four Zn^II 5,10,15-triphenylporphyrin (TriPP) complexes meso-meso linked by two-atom bridges, namely, C₂H₂ (2), C₂ (3), CH=N (4), and N₂ (5), were prepared, for comparison of ground-state inter-porphyr

Full text of DOI:10.1002/ejoc.201500183

Eur. J. Org. Chem. 2015 · ISSN 1099–0682
SUPPORTING INFORMATION
DOI: 10.1002/ejoc.201500183
Title: Synthetic, Structural, and Spectroscopic Studies of Bis(porphyrinzinc) Complexes Linked by Two-Atom
Conjugating Bridges
Author(s): Shannon R. Harper, Michael C. Pfrunder, Louisa J. Esdaile, Paul Jensen, John C. McMurtrie, Dennis P.
Arnold*

Table of Contents
NMR Spectra of novel porphyrins in CDCl (resonances for residual CHCl and water at ca. 1.5
3
3
ppm present in all spectra; CH Cl residues present in some samples, other impurities noted on
2
2
spectra) and high resolution mass spectra for novel diporphyrins.
S2-S19
Figure S1. The hydrogen bonded cyclic hexamer in the crystal structure of the zinc formylporphyrin
3. S20
2
Figure S2. Effects of solvents on the Soret band region of the electronic absorption spectrum of
imine diporphyrin 4: (a) the Soret band region; (b) the Q band region. S21
Figure S3. Fluorescence emission spectra in toluene: (a) ethyne 3 excited at 414 nm (solid), 482 nm
(
dots), and absorption spectrum scaled for convenience (dashes); (b) imine 4 excited at 427 nm
solid), 449 nm (dots), and absorption spectrum scaled for convenience (dashes). S22
(

S2
ZnTriPPI 24
Ph
N
N
N
N
Ph
Zn
I
Ph
H TriPPCHO 33
2
Ph
NH
N
N
Ph
CHO
HN
Ph

S3
NiTriPPCH OH 8
2
Ph
N
N
N
N
Ph
Ni
CH OH
2
Ph

S4
NiTriPPCH CH 17 (* = NiTriPP 6)
2
3
Ph
N
N
N
N
Ph
Ni
CH2CH3
Ph
ZnTriPPCH CH Ph 18 (* = aliphatic hydrocarbon residues)
2
2
Ph
N
N
N
Ph
Zn
N
Ph

S5
ZnTriPPCHO 23 (pyridine coordinated)
Ph
N
N
N
N
Ph
Zn
CHO
Ph

S6
H TriPPNH 30
2
2
Ph
NH
N
N
Ph
NH
2
HN
Ph

S7
ZnTriPP–C –ZnTriPP 26 (pyridine coordinated; * = ZnTriPP–C –ZnTriPP 3; aliphatic
4
2
hydrocarbon residues present)
Ph
Ph
Zn
Ph
N
N
N
N
N
N
N
N
Ph
Zn
Ph
Ph
HRMS (MALDI)
Applied Biosystems 4700 Proteomics Analyzer 66
4
700 Reflector Spec #1 MC=>MC[BP = 1250.3, 656]
1250.2589
100
656.5
90
80
70
60
50
40
30
20
10
1
248.2582
1249.2621
1252.2540
1246.2601
1254.2618
1255.2572
1258.2640
1260.5610
0
1
243.0
1247.2
1251.4
1255.6
1259.8
1264.0
Mass (m/z)

S8
NiTriPP–CH=N–NiTriPP 29 (aliphatic hydrocarbon residues present)
Ph
Ph
N
N
N
N
N
N
N
N
Ph
Ni
CH
N
Ni
Ph
Ph
Ph

S9
COSY
NOESY

S10
HRMS (MALDI)
Applied Biosystems 4700 Proteomics Analyzer 66
4
700 Reflector Spec #1 MC=>MC[BP = 1216.3, 7491]
1
216.2744
100
1
214.2789
7491.2
90
80
70
60
50
40
30
20
10
1
217.2737
1218.2710
1
213.2733
1220.2637
1
212.2681
1
211.2632
1223.2574
1
209.2609
1226.2301
1229.2549
1232.0
1206.2805
0
1
198.0
1204.8
1211.6
1218.4
1225.2
Mass (m/z)

S11
ZnTriPP–CH=N–H TriPP 31 (minor porphyrin impurities, some coordinated pyridine and
2
aliphatic hydrocarbon and other residues present)
Ph
Ph
N
N
N
N
N
HN
N
Ph
Zn
CH
N
Ph
NH
Ph
Ph
H TriPP–CH=N–H TriPP 32 (aliphatic hydrocarbon and other residues present)
2
2
Ph
Ph
NH
N
N
N
HN
Ph
CH
N
Ph
HN
NH
N
Ph
Ph

S12
InXTriPP–CH=N–H TriPP 35 (aliphatic hydrocarbon and other residues present)
2
COSY

S13
NOESY (the peaks marked with arrows are positive contours, i.e. EXSY cross-peaks showing
exchange between ortho-phenyl protons on the lateral phenyl groups on the indium(III) ring)
HRMS (MALDI)
Applied Biosystems 4700 Proteomics Analyzer 66
4
700 Reflector Spec #1 MC=>MC=>MC[BP = 1214.3, 2340]
1214.3074
100
2340.1
90
80
70
60
50
40
30
20
10
1216.6229
1
213.2969
1233.5880
1231.3313
1238.2861
1234.8
1
220.3110
1
209.6404
0
1
178.0
1192.2
1206.4
1220.6
1249.0
Mass (m/z)

S14
ZnTriPP–CH=CH–ZnTriPP 2
Ph
Ph
M
N
N
N
N
N
N
N
N
Ph
Zn
Ph
Ph
Ph

S15
ZnTriPP–C –ZnTriPP 3 (pyridine coordinated)
2
Ph
Ph
Zn
Ph
N
N
N
N
N
N
N
N
Ph
Zn
Ph
Ph
COSY

S16
NOESY
HRMS (MALDI)
Applied Biosystems 4700 Proteomics Analyzer 66
4
700 Reflector Spec #1 MC=>MC[BP = 2466.2, 5848]
1226.2195
100
685.0
90
80
70
60
50
40
30
20
10
1224.2203
1225.2233
1
227.2218
1228.2253
1
223.2263
222.2146
1
1
233.5621
1
233.0546
1
220.2900
1230.2318
1
220.6173
1
219.9476
1230.9337
1239.2455
1237.2266
1242.2346
0
1
214.0
1220.2
1226.4
1232.6
1238.8
1245.0
Mass (m/z)

S17
ZnTriPP–CH=N–ZnTriPP 4 (pyridine coordinated)
Ph
Ph
Zn
Ph
N
N
N
N
N
N
N
N
Ph
Zn
CH
N
Ph
Ph

S18
COSY
NOESY

S19
HRMS (ESI)
ZnTriPP–N=N–ZnTriPP 5 (in CDCl + C D N; * = water in exchange with pyridine)
3
5
5
Ph
Ph
M
N
N
N
N
N
N
N
N
Ph
Zn
N
N
Ph
Ph
Ph

S20
Figure S1. The hydrogen bonded cyclic hexamer in the crystal structure of the zinc formylporphyrin
2
3.

S21
Figure S2. Effects of solvents on the Soret band region of the electronic absorption spectrum of
imine diporphyrin 4: (a) the Soret band region; (b) the Q band region.
3
(
a)
250x10
Znimine_tol
Znimine_DCM
Znimine_EA
2
1
1
00
Znimine_DMF
Znimine_MeOH
Znimine_py
Znimine_MeCN
50
00
50
0
400
420
440
460
480
500
520
Wavelength/nm
(b)
3
40x10
Znimine_tol
Znimine_DCM
Znimine_EA
Znimine_DMF
Znimine_MeOH
Znimine_py
3
2
1
0
Znimine_MeCN
0
0
0
600
700
800
900
Wavelength/nm

S22
Figure S3. Fluorescence emission spectra in toluene: (a) ethyne 3 excited at 414 nm (solid), 482 nm
(dots), and absorption spectrum scaled for convenience (dashes); (b) imine 4 excited at 427 nm
(solid), 449 nm (dots), and absorption spectrum scaled for convenience (dashes).
(
a)
100
80
60
40
20
0
400
500
600
700
800
900
Wavelength/nm
(b)
1
.2
.0
.8
.6
.4
.2
.0
1
0
0
0
0
0
400
500
600
700
800
Wavelength/nm