Supporting Information for:

Synthesis and photophysical properties of phosphorus (V)

porphyrins functionalized with axial carbazolylvinylnaphthalimides

Yong Zhan,a Kaiyu Cao,a Chenguang Wang,a Junhui Jia,a Pengchong Xue,a Xingliang Liu,a Xuemei Duan,b Ran Lu a,*

a State Key Laboratory of Supramolecular Structure and Materials, College of Chemistry, Jilin University, Changchun 130012, P. R. China.

b State Key Laboratory of Theoretical and Computational Chemistry, Institute of

Theoretical Chemistry, Jilin University, Changchun 130021, P. R. China.

Fax: +86-431-88923907; Tel: +86-431-88499179

E-Mail: luran@mail.jlu.edu.cn

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Table S1. Photophysical data of phosphorus (V) porphyrins 1, 2 and 12. Absorption (λmax/nm) (ε×10-4/M-1 cm-1)a Emission(nm)b

Compound Soret Q1 Q2

1 300 (7.51) 350 (5.05) 440 (26.25) 564 (1.94) 611(1.00) 620, 672

2 300 (7.69) 350 (8.20) 440 (16.60) 564 (1.40) 610 (0.64) 620, 672

12 300 (0.44) 350 (0.35) 437 (5.71) 563 (0.45) 606 (0.34) 618, 669 a measured in CHCl3 (1.0×10-6 M) at room temperature. b measured in CHCl3 (1.0×10-6 M) at room temperature, excited at 570 nm.

Fig. S1 Normalized (a) UV-vis absorption and (b) Fluorescence emission spectra of compound 8 in different solvents (1.0 × 10-6 M, ex = 440 nm).

Fig. S2 Normalized UV-vis absorption of (a) phosphorus (V) porphyrins 1 and 12 (5.0 × 10-6 M), and compound 8 (1.0 × 10-5 M) in chloroform; (b) phosphorus (V) porphyrins 2 and 12 (5.0 × 10-6 M), and compound 9 (1.0 × 10-5 M) in chloroform.

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Fig. S3 Normalized UV-vis absorption spectra of phosphorus (V) porphyrins 1 and 2 in the film.

Fig. S4 Cyclic voltammogram diagrams of phosphorus (V) porphyrins 1 and 2 in anhydrous CH2Cl2 with 0.1 M Bu4NBF4 as electrolyte at a scan rate of 100 mV s-1.

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N

CHO

Fig. S5 1H-NMR (300 MHz, CDCl3) spectrum of compound 3.

N

CHO

Fig. S6 MALDI/TOF MS spectrum of compound 3.

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N

CHOI

Fig. S7 1H-NMR (300 MHz, CDCl3) spectrum of compound 4.

N

CHOI

Fig. S8 MALDI/TOF MS spectrum of compound 4.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

N

CHO

N

Fig. S9 1H-NMR (500 MHz, CDCl3) spectrum of compound 6.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

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%Int.

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173 mV[sum= 3106 mV] Profiles 24-41 Smooth Av 20 -Baseline 80

Reflectron Mode Data: LR-216-L0001.L18 14 Oct 2011 11:36 Cal: 31 Oct 2011 19:16 Kratos PC Axima CFR V2.3.1: Mode default_linear, Power: 40, P.Ext. @ 610 (bin 57)

610.8

N

N

CHO

Fig. S10 MALDI/TOF MS spectrum of compound 6.

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N

N

Fig. S11 1H-NMR (500 MHz, CDCl3) spectrum of compound 7.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

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356 mV[sum= 13885 mV] Profiles 1-39 Smooth Av 20 -Baseline 80

Reflectron Mode Data: LR169-L0001.H7 31 May 2011 10:05 Cal: 2 Jan 2002 16:12 Kratos PC Axima CFR V2.3.1: Mode default_linear, Power: 90, P.Ext. @ 608 (bin 57)

608.5

N

N

Fig. S12 MALDI/TOF MS spectrum of compound 7.

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N

O

O

OMeNC8H17

Fig. S13 1H-NMR (300 MHz, CDCl3) spectrum of compound 8.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

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432 mV[sum= 9502 mV] Profiles 17-38 Smooth Av 20 -Baseline 80

Reflectron Mode Data: LR208-L0001.F17 20 Sep 2011 11:13 Cal: 2 Jan 2002 23:30 Kratos PC Axima CFR V2.3.1: Mode default_linear, Power: 50, P.Ext. @ 606 (bin 57)

607.6

477.7

464.1

N N

O

O

OMe

Fig. S14 MALDI/TOF MS spectrum of compound 8.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

N

N

C8H17

C8H17

N

O

O

OMe

Fig. S15 1H-NMR (300 MHz, CDCl3) spectrum of compound 9.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

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458 mV[sum= 10980 mV] Profiles 1-24 Smooth Av 20 -Baseline 80

Reflectron Mode Data: LR209-L0001.G17 20 Sep 2011 11:14 Cal: 2 Jan 2002 23:31 Kratos PC Axima CFR V2.3.1: Mode default_linear, Power: 50, P.Ext. @ 910 (bin 57)

910.8

477.7 636.2

N

N

NO

OOMe

Fig. S16 MALDI/TOF MS spectrum of compound 9.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

Fig. S17 1H-NMR (300 MHz, CDCl3) spectrum of compound 10.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

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155 mV[sum= 2936 mV] Profiles 1-19 Smooth Av 20 -Baseline 80

Reflectron Mode DKr

ata: 2470001.N22 4 Nov 2011 14:56 Cal: 4 Nov 2011 15:18 atos PC Axima CFR V2.3.1: Mode default_linear, Power: 60, P.Ext. @ 592 (bin 57)

593.3

Fig. S18 MALDI/TOF MS spectrum of compound 10.

Fig. S19 1H-NMR (300 MHz, DMSO-d6) spectrum of compound 11.

608.7

N N

O

O

OH

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316 mV[sum= 11372 mV] Profiles 44-79 Smooth Av 20 -Baseline 80

Reflectron Mode Data: LR133-R0001.J3 29 Apr 2011 10:45 Cal: 18 Jan 2002 7:58 Kratos PC Axima CFR V2.3.1: Mode default_reflectron, Power: 90, P.Ext. @ 896 (bin 82)

896.5

N

N

NO

OOH

Fig. S20 MALDI/TOF MS spectrum of compound 11.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

N

N

O

O

ON

NN

NP

N

N

O

O

O

Fig. S21 1H-NMR (600 MHz, CDCl3) spectrum of compound 1.

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Fig. S22 13C-NMR (75 MHz, CDCl3) spectrum of compound 1.

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60 mV[sum= 4998 mV] Profiles 25-108 Smooth Av 20 -Baseline 80

Reflectron Mode Data: LR167-L0001.J7 31 May 2011 10:02 Cal: 2 Jan 2002 16:02 Kratos PC Axima CFR V2.3.1: Mode default_linear, Power: 100, P.Ext. @ 1825 (bin 57)

1827.6

1523.2

N

N

O

O

ON

NN

NP

N

N

O

O

O

Fig. S23 MALDI/TOF MS spectrum of compound 1. Fig. S23 MALDI/TOF MS spectrum of compound 1.

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Fig. S24 High resolution mass spectrum of compound 1.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012

N

N

N

O

O

ON

NN

NP

N

N

N

O

O

O

Fig. S25 1H-NMR (600 MHz, CDCl3) spectrum of compound 2.

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Fig. S26 13C-NMR (125 MHz, CDCl3) spectrum of compound 2.

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83 mV[sum= 8169 mV] Profiles 34-131 Smooth Av 20 -Baseline 80

Reflectron Mode Data: LR168-L0001.I7 31 May 2011 10:04 Cal: 2 Jan 2002 16:10 Kratos PC Axima CFR V2.3.1: Mode default_linear, Power: 90, P.Ext. @ 2432 (bin 58)

2434.5

2159.1 2450.9

N

N

N

O

O

ON

NN

NP

N

N

N

O

O

O

Fig. S27 MALDI/TOF MS spectrum of compound 2.

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Fig. S28 High resolution mass spectrum of compound 2.

Electronic Supplementary Material (ESI) for Organic & Biomolecular ChemistryThis journal is © The Royal Society of Chemistry 2012