Supporting Information

Transcription

1 Supporting Information Four Di-butylamino Substituents Are Better than Eight in Modulating the Electronic Structure and Third-order NLO Properties of Phthalocyanines Yuxiang Chen, Wei Cao, Chiming Wang, Dongdong Qi,,* Kang Wang, and Jianzhuang Jiang,*

2 Content The validity of the functional τhcthhyb. Systematic comparison between the cyclic voltammograms for M{Pc[N(C 4 H 9 ) 2 ] 4 } and M{Pc[N(C 4 H 9 ) 2 ] 8 }. References for Supporting Information Figure SS1. The experimental and calculated vertical excitation energies for H 2 {Pc[N(C 4 H 9 ) 2 ] 4 } (the experimental spectrum was recorded in CHCl 3 solution). Figure SS2. The comparison of cyclic voltammograms for M{Pc[N(C 4 H 9 ) 2 ] 4 } and M{Pc[N(C 4 H 9 ) 2 ] 8 }. Table SS1. Comparison between the calculated and experimental excitation energy of H 2 {Pc[N(C 4 H 9 ) 2 ] 4 }. Table SS2. The LCI (linear convolution integral) analysis to the CV diagrams. Figure S1. Experimental and simulated isotopic patterns for 1-5.

3 Figure S2. 1 H NMR spectrum of 1 recorded in CD 2 Cl 2 /80% N 2 H 4 H 2 O (v/v = 100/1) at 25 C. Figure S3. 1 H NMR spectrum of 2 recorded in CD 2 Cl 2 /80% N 2 H 4 H 2 O (v/v = 100/1) at 25 C. Figure S4. 1 H NMR spectrum of 3 recorded in CD 2 Cl 2 /80% N 2 H 4 H 2 O (v/v = 100/1) at 25 C. Figure S5. 1 H NMR spectrum of 5 recorded in CD 2 Cl 2 /80% N 2 H 4 H 2 O (v/v = 100/1) at 25 C. Figure S6. Electronic absorption spectra of M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Mg, Ni, Cu, Zn) (1-5) in CHCl 3. Figure S7. IR spectra of M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Mg, Ni, Cu, Zn) (1-5). Figure S8. Cyclic voltammograms of 1-5 (from top to bottom) in CH 2 Cl 2 containing 0.1 mol dm 3 [Bu 4 N][ClO 4 ] at a scan rate of 30 mv s 1. Table S1. Analytical and mass spectrometric data for 1-5.

4 Table S2. 1 H NMR data (δ) for 1, 2, 3, and 5 recorded with the concentration of ca M in CD 2 Cl 2 /80% N 2 H 4 H 2 O (v/v = 100/1) at 25 C. Table S3. Crystal data and structure refinements for 4-(dibutylamino)phthalonitrile and 4,5-bis(dibutylamino)phthalonitrile. Table S4. The two dihedral angles Φ 1 and Φ 2 for 4-(dibutylamino)phthalonitrile and 4,5-bis(dibutylamino)phthalonitrile. Table S5. The two dihedral angles Φ 1 and Φ 2 for M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Zn) and M{Pc[N(C 4 H 9 ) 2 ] 8 } (M = 2H, Zn). Table S6. Electron density difference plots of electron transitions for MPc (M = 2H, Zn). Table S7. Electron density difference plots of electron transitions for M{Pc[N(C 4 H 9 ) 2 ] 8 } (M = 2H, Zn). Table S8. Electron density difference plots of electron transitions for M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Zn). Table S9. The molecular orbital maps with their energy levels for MPc, M{Pc[N(C 4 H 9 ) 2 ] 8 }, and M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Zn).

5 The validity of the functional τhcthhyb In all cases, density functional theory (DFT) calculations with B3LYP 1 and time dependent density functional theory (TDDFT) calculations with τhcthhyb 2 were used to optimize geometry and simulate the electronic absorption. In order to provide more reasonable TDDFT calculating results, twelve different functionals including B3PW91, 1a,3 BB1K, 4 LC-HCTH147, 5 LC-τHCTH, 5d,6 M11, 7 M06-2X, 8 τhcthhyb, τhcth, 6 ωb97x, 9 B3LYP, PBE, 10 and MPW1KCIS, 11 have been employed to study the transition energies and the transition natures of MPc (M = 2H, Zn), M{Pc[N(C 4 H 9 ) 2 ] 8 } (M = 2H, Zn), and M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Zn). The LanL2DZ basis set for Zn atom and 6-31G(d) basis set for all the other atoms were employed. 12 All calculations were carried out using Gaussian 09 D.01 program. 13 Comparison of the results obtained by the twelve different levels of theory with the experiment is shown in Figure SS1 and tabulated in Table SS1 (Supporting Information). The experimental electronic absorption peaks of H 2 {Pc[N(C 4 H 9 ) 2 ] 4 } recorded in CHCl 3 are located in 1.62, 2.40, and 2.68 ev, respectively. As can be found in Figure SS1 and Table SS1 (Supporting Information), the experimentally revealed broad Q band of H 2 {Pc[N(C 4 H 9 ) 2 ] 4 } at 1.62 ev is overestimated by all the methods except the τhcth one. The τhcth method is underestimated by nearly 0.11 ev. In detail, the difference between the calculated and experimental data is 0.20 ev for B3PW91, 0.32 ev for BB1K, 0.15 ev for LC-HCTH147, and 0.07 ev for LC-τHCTH, 0.24 ev for M11, 0.35 ev for M06-2X, 0.15 ev for τhcthhyb, 0.11 ev for τhcth, 0.19 ev for ωb97x, 0.20 ev for B3LYP, 0.31 ev for PBE, and 0.18 ev for

6 MPW1KCIS, respectively, revealing that LC-HCTH147, LC-τHCTH, and τhcthhyb tend to provide better excitation energies in the low-energy Q-band region. Experimentally, the two new peaks were observed for H 2 {Pc[N(C 4 H 9 ) 2 ] 4 } at 2.40 and 2.68 ev due to the introduction of peripheral dibutylamino substituents. Similarly, calculation with B3PW91, τhcthhyb, τhcth, and B3LYP functionals indicates obvious absorption at 2.36/2.79, 2.23/2.68, 1.88/2.36, and 2.37/2.79 ev, respectively, while other functionals do not predict these typical peaks, Figure SS1 and Table SS1 (Supporting Information). As detailed above, the hgga functional τhcthhyb provides an overall improvement in predicting the electronic absorption spectrum of H 2 {Pc[N(C 4 H 9 ) 2 ] 4 } in nm region, which could well explain the red-shift of the Q band and the broad absorption band in nm. As a result, TDDFT calculations with τhcthhyb are applied to simulate the molecular orbitals and electronic absorption spectra of the whole series of metal-free and zinc compounds of phthalocyanines possessing dibutylamino at the phthalocyanine periphery in our text.

7 Systematic comparison between the cyclic voltammograms for M{Pc[N(C 4 H 9 ) 2 ] 4 } and M{Pc[N(C 4 H 9 ) 2 ] 8 } In order to deeply comprehend the nature of first oxidation potential in the cyclic voltammograms for M{Pc[N(C 4 H 9 ) 2 ] 4 } and M{Pc[N(C 4 H 9 ) 2 ] 8 } (M = 2H, Mg, Cu, Zn), the first oxidation potential peak is split out by the cubic curve tangent to the main CV curve at the starting point (A or D) and the end point (C or F), Figure SS2 (Supporting Information). 14 As can be found, the first oxidation potential range is -0.20~+0.63 V for H 2 {Pc[N(C 4 H 9 ) 2 ] 4 }, -0.47~+0.48 V for Mg{Pc[N(C 4 H 9 ) 2 ] 4 }, -0.39~+0.68 V for Cu{Pc[N(C 4 H 9 ) 2 ] 4 }, and -0.54~+0.38 V for Zn{Pc[N(C 4 H 9 ) 2 ] 4 }, respectively. In comparison, the first oxidation potential range of their counterparts is +0.20~+0.73 V for H 2 {Pc[N(C 4 H 9 ) 2 ] 8 }, -0.30~+0.34 V for Mg{Pc[N(C 4 H 9 ) 2 ] 8 }, -0.08~+0.61 V for Cu{Pc[N(C 4 H 9 ) 2 ] 8 }, and -0.30~+0.45 V for Zn{Pc[N(C 4 H 9 ) 2 ] 8 }, respectively. The overall comparison between the first oxidation potential of these counterparts clearly indicates the lower first oxidation potential of M{Pc[N(C 4 H 9 ) 2 ] 4 } and the higher first oxidation potential of M{Pc[N(C 4 H 9 ) 2 ] 8 }, leading to the significant reducibility of M{Pc[N(C 4 H 9 ) 2 ] 4 } in its chloroform solution.

8 References for Supporting Information [1] (a) Becke, A. D. J. Chem. Phys. 1993, 98, (b) Lee, C.; Yang, W.; Parr, R. G. Phys. Rev. B. 1988, 37, (c) Miehlich, B.; Savin, A.; Stoll, H.; Preuss, H. Chem. Phys. Lett. 1989, 157, [2] Boese, A. D.; Handy, N. C. J. Chem. Phys. 2002, 116, [3] (a) Ziesche, P., Eschrig, H. Eds. Electronic Structure of Solids '91 : Proceedings of the 75th WE-Heraeus-Seminar; Akademie Verlag: Berlin, (b) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B. 1992, 46, (c) Perdew, J. P.; Chevary, J. A.; Vosko, S. H.; Jackson, K. A.; Pederson, M. R.; Singh, D. J.; Fiolhais, C. Phys. Rev. B. 1993, 48, (d) Perdew, J. P.; Burke, K.; Wang, Y. Phys. Rev. B 1996, 54, (e) Dobson, J. F., Vignale, G., Das, M. P. Eds. Electronic Density Functional Theory: Recent Progress and New Directions. Plenum Press: New York, [4] (a) Becke, A. D. Phys. Rev. A. 1988, 38, (b) Becke, A. D. J. Chem. Phys. 1996, 104, [5] (a) Hamprecht, F. A.; Cohen, A. J.; Tozer, D. J.; Handy, N. C. J. Chem. Phys. 1998, 109, (b) Boese, A. D.; Doltsinis, N. L.; Handy, N. C.; Sprik, M. J. Chem. Phys. 2000, 112, (c) Boese, A. D.; Handy, N. C. J. Chem. Phys. 2001, 114, (d) Iikura, H.; Tsuneda, T.; Yanai, T.; Hirao, K. J. Chem. Phys. 2001, 115, [6] Boese, A. D.; Handy, N. C. J. Chem. Phys. 2002, 116, [7] Peverati, R.; Truhlar, D. G. J. Phys. Chem. Lett. 2011, 2,

9 [8] Zhao, Y.; Truhlar, D. G. Theor. Chem. Acc. 2008, 120, [9] Chai, J.; Head-Gordon, M. J. Chem. Phys. 2008, 128, [10] Ernzerhof, M.; Perdew, J. P. J. Chem. Phys. 1998, 109, [11] (a) Rey, J.; Savin, A. Int. J. Quantum Chem. 1998, 69, (b) Gonis, A., Kioussis, N., Ciftan, M. Eds. Electron Correlations and Materials Properties, Kluwer Academic: New York, 1999 (c) VanDoren, V., VanAlsenoy, C., Geerlings, P. Eds. Density Functional Theory and its Application to Materials, A.I.P. Conference Proceedings: New York, 2001; Vol. 577 (d) Toulouse, J.; Savin, A.; Adamo, C. J. Chem. Phys. 2002, 117, (e) Adamo, C.; Barone, V. J. Chem. Phys. 1998, 108, [12] (a) P. J. Hay.; W. R. Wadt. J. Chem. Phys. 1985, 82, (b) P. J. Hay.; W. R. Wadt. J. Chem. Phys. 1985, 82, (c) W. R. Wadt.; P. J. Hay. J. Chem. Phys. 1985, 82, [13] Frisch, M. J., Trucks, G. W., Schlegel, H. B., Scuseria, G. E., Robb, M. A., Cheeseman, J. R., Scalmani, G., Barone, V., Mennucci, B., Petersson, G. A., Nakatsuji, H., Caricato, M., Li, X., Hratchian, H. P., Izmaylov, A. F., Bloino, J., Zheng, G., Sonnenberg, J. L., Hada, M., Ehara, M., Toyota, K., Fukuda, R., Hasegawa, J., Ishida, M., Nakajima, T., Honda, Y., Kitao, O., Nakai, H., Vreven, T., Montgomery, J. A., Jr., Peralta, J. E., Ogliaro, F., Bearpark, M., Heyd, J. J., Brothers, E., Kudin, K. N., Staroverov, V. N., Kobayashi, R., Normand, J., Raghavachari, K., Rendell, A., Burant, J. C., Iyengar, S. S., Tomasi, J., Cossi, M., Rega, N., Millam, J. M., Klene, M., Knox, J. E., Cross, J. B., Bakken, V., Adamo, C., Jaramillo, J., Gomperts, R., Stratmann, R. E., Yazyev, O., Austin, A. J., Cammi, R., Pomelli, C., Ochterski, J. W., Martin, R. L., Morokuma, K., Zakrzewski, V. G., Voth, G. A., Salvador, P., Dannenberg, J. J., Dapprich, S., Daniels, A. D., Farkas, Ö.,

10 Foresman, J. B., Ortiz, J. V., Cioslowski, J., Fox, D. J. Gaussian 09, revision D.01, Gaussian, Inc.: Pittsburgh, PA, [14] Zhang, R. Scientific Computing with Python, Chapter 3, pp , Tsinghua University Press, 2012.

11 Figure SS1. The experimental and calculated vertical excitation energies for H 2 {Pc[N(C 4 H 9 ) 2 ] 4 } (the experimental spectrum was recorded in CHCl 3 solution).

12 Figure SS2. The comparison of cyclic voltammograms for M{Pc[N(C 4 H 9 ) 2 ] 4 } and M{Pc[N(C 4 H 9 ) 2 ] 8 }. (M = 2H, Mg, Cu, Zn).

13 Table SS1. Comparison between the calculated and experimental excitation energy of H 2 {Pc[N(C 4 H 9 ) 2 ] 4 }. Calculated excitation energy (ev), oscillator strength (f), and configurations in vacuum system are displayed. Excitation energy between 1.5 and 3.0 ev, f > , and configurations which contribute more than 10% are shown. (Assignment: S = excited state, S1 = the first excited state, S2 = the second excited state, S3 = the third excited state, etc.) Experiment Peak: 1.62 ev Peak: 2.40 ev Peak: 2.68 ev B3PW91 BB1K LC-HCTH147 LC-τHCTH M11 M06-2X τhcthhyb τhcth ωb97x E = 1.82 ev f = S1 E = 1.95 ev f = S1 E = 1.78 ev f = S1 E = 1.69 ev f = S1 E = 1.87 ev f = S1 E = 1.97 ev f = S1 E = 1.76 ev f = S1 E = 1.51 ev f = S1 E = 1.81 ev f = S1 E = 1.86 ev f = S2 E = 2.36 ev f = S3 E = 2.79 ev f = S4 E = 1.99 ev f = S E = 1.76 ev f = S2 E = 1.94 ev f = S2 E = 2.02 ev f = S2 E = 1.80 ev E = 2.23 ev E = 2.68 ev f = f = f = S2 S3 S4 E = 1.57 ev E = 1.89 ev E = 2.36 ev f = f = f = S2 S3 S4 E = 1.88 ev f = S2

14 E = 1.82 ev E = 1.87 ev E = 2.37 ev E = 2.79 ev B3LYP f = f = f = f = S1 E = 1.93 ev S2 E = 1.98 ev S3 S4 PBE f = f = S1 E = 1.80 ev S2 E = 1.84 ev MPW1KCIS f = f = S1 S2

15 Table SS2. The LCI (linear convolution integral) analysis to the CV diagrams. Here, PnU/PnL (n = 1, 2, 3, 4) is the abbreviate of the nth Peak in the Upper/Lower curve. The Oxd 1 data can be calculated according to Pn = (PnU + PnL) / 2, n = 1, 2, 3, 4. LCI analysis to the CV Diagrams Oxd 1 of Independent Peaks P 1 = 0.07 V P 2 = 0.12 V P 3 = 0.22 V P 4 = 0.35 V P 1 = V P 2 = 0.09 V P 3 = 0.16 V P 4 = 0.27 V P 1 = V P 2 = 0.10 V P 3 = 0.23 V P 4 = 0.38 V P 1 = V P 2 = 0.06 V P 3 = 0.23 V P 4 = 0.39 V

16 P 1 = V P 2 = V P 3 = 0.05 V P 4 = 0.15 V

17 Figure S1. (a) Experimental and (b) simulated isotopic patterns for 1; (c) Experimental and (d) simulated isotopic patterns for 2; (e) Experimental and (f) simulated isotopic patterns for 3; (g) Experimental and (h) simulated isotopic patterns for 4; (i) Experimental and (j) simulated isotopic patterns for 5.

18 Figure S2. 1 H NMR spectrum of H 2 {Pc[N(C 4 H 9 ) 2 ] 4 } (1) recorded in CD 2 Cl 2 /80% N 2 H 4 H 2 O (v/v = 100/1) at 25 C. The signals due to residual CH 2 Cl 2 and N 2 H 4 H 2 O are denoted as * and #, respectively.

19 Figure S3. 1 H NMR spectrum of Mg{Pc[N(C 4 H 9 ) 2 ] 4 } (2) recorded in CD 2 Cl 2 /80% N 2 H 4 H 2 O (v/v = 100/1) at 25 C. The signals due to residual CH 2 Cl 2 and N 2 H 4 H 2 O are denoted as * and #, respectively.

20 Figure S4. 1 H NMR spectrum of Ni{Pc[N(C 4 H 9 ) 2 ] 4 } (3) recorded in CD 2 Cl 2 /80% N 2 H 4 H 2 O (v/v = 100/1) at 25 C. The signals due to residual CH 2 Cl 2 and N 2 H 4 H 2 O are denoted as * and #, respectively.

21 Figure S5. 1 H NMR spectrum of Zn{Pc[N(C 4 H 9 ) 2 ] 4 } (5) recorded in CD 2 Cl 2 /80% N 2 H 4 H 2 O (v/v = 100/1) at 25 C. The signals due to residual CH 2 Cl 2 and N 2 H 4 H 2 O are denoted as * and #, respectively.

22 Figure S6. Electronic absorption spectra of M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Mg, Cu, Ni, Zn) (1-5) in CHCl 3.

23 Figure S7. IR spectra of M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Mg, Cu, Ni, Zn) (1-5).

24 Figure S8. Cyclic voltammograms of 1-5 in CH 2 Cl 2 containing 0.1 M [Bu 4 N][ClO 4 ] at a scan rate of 30 mv s 1.

25 Table S1. Analytical and mass spectrometric data for 1-5. a compound (M) + (m/z) Analysis C H N (1022.7) b (74.16) c 8.24 (8.42) c (16.18) c (1044.7) b (70.07) d 7.86 (7.79) d (15.03) d (1078.6) b (67.99) e 7.58 (7.53) e (14.69) e (1083.6) b (69.16) f 7.58 (7.78) f (14.95) f (1084.6) b (68.60) g 7.58 (7.59) g (14.88) g [a] Calculated values given in parentheses. [b] By MALDI-TOF mass spectrometry. [c] Contain equiv. solvated CH 2 Cl 2 and 0.25 equiv. solvated H 2 O. [d] Contain 0.75 equiv. solvated CH 2 Cl 2 and equiv. solvated THF. [e] Contain 0.75 equiv. solvated CH 2 Cl 2. [f] Contain equiv. solvated H 2 O, 0.25 equiv. solvated CH 2 Cl 2 and 0.5 equiv. solvated CH 3 OH. [g] Contain 0.75 equiv. solvated CH 2 Cl 2.

26 Table S2. 1 H NMR data (δ) for 1, 2, 3, and 5 recorded with the concentration of ca M in CD 2 Cl 2 /80% N 2 H 4 H 2 O (v/v = 100/1) at 25 C. NH Ar-H n-bu CH 2 CH 2 CH 2 CH (m, 2 H) (m, 4 H) (m, 4 H) (m, 4 H) (m, 16 H) (m, 16 H) (m, 16 H) (m, 24 H) (m, 4 H) (m, 4 H) (m, 4 H) (m, 16 H) (m, 16 H) (m, 16 H) (m, 24 H) (m, 4 H) (m, 4 H) (m, 4 H) (m, 16 H) (m, 16 H) (m, 16 H) (m, 24 H) (t, 4 H) (d, 4 H) (d, 4 H) (t, 16 H) (m, 16 H) (m, 16 H) (t, 24 H)

27 Table S3. Crystal data and structure refinements for 4-(dibutylamino)phthalonitrile (a) and 4,5-bis(dibutylamino)phthalonitrile (b). Compound a b formula C 16 H 21 N 3 C 24 H 38 N 4 fw crystal system monoclinic monoclinic space group P2 1 /c P2 1 /c a (3) (14) b (12) (10) c (3) (18) α β (18) (11) γ V (5) (4) Z 4 4 θ range (deg) F calcd (g/cm 3 ) µ(mm -1 ) F(000) R 1 (I>2θ) R w2 (I>2θ) R w2 for all GOF on F CCDC number

28 Table S4. The two dihedral angles Φ 1 and Φ 2 for 4-(dibutylamino)phthalonitrile and 4,5- bis(dibutylamino)phthalonitrile. Precursors The dihedral angles Φ Φ Φ Φ Φ Φ

29 Table S5. The two dihedral angles Φ 1 and Φ 2 for M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Zn) and M{Pc[N(C 4 H 9 ) 2 ] 8 } (M = 2H, Zn). Fragment A Fragment B Fragment C Fragment D M=2H, R 2 =R 3 =R 5 =R 7 =H Φ R 1 =R 4 =R 6 =R 8 = N(C 4 H 9 ) 2 Φ M=2H, R 2 =R 3 =R 5 =R 8 =H Φ R 1 =R 4 =R 6 =R 7 = N(C 4 H 9 ) 2 Φ M=2H, R 2 =R 3 =R 6 =R 7 =H Φ R 1 =R 4 =R 5 =R 8 = N(C 4 H 9 ) 2 Φ M=2H, R 2 =R 4 =R 6 =R 8 =H Φ R 1 =R 3 =R 5 =R 7 = N(C 4 H 9 ) 2 Φ M=Zn, R 2 =R 3 =R 5 =R 7 =H Φ R 1 =R 4 =R 6 =R 8 = N(C 4 H 9 ) 2 Φ M=Zn, R 2 =R 3 =R 5 =R 8 =H Φ R 1 =R 4 =R 6 =R 7 = N(C 4 H 9 ) 2 Φ M=Zn, R 2 =R 3 =R 6 =R 7 =H Φ R 1 =R 4 =R 5 =R 8 = N(n-C 4 H 9 ) 2 Φ M=Zn, R 2 =R 4 =R 6 =R 8 =H Φ R 1 =R 3 =R 5 =R 7 = N(C 4 H 9 ) 2 Φ M=2H R 1 =R 2 =R 3 =R 4 =R 5 =R 6 =R 7 =R 8 = N(C 4 H 9 ) 2 M=Zn R 1 =R 2 =R 3 =R 4 =R 5 =R 6 =R 7 =R 8 = N(C 4 H 9 ) 2 Φ 1 Φ 2 Φ 1 Φ

30 Table S6. Electron density difference plots of electron transitions (isovalue: e au -3 ) for H 2 Pc and ZnPc. Electron densities move from the cyan area to the purple area. Excited states with less than cm -1 and configurations which contribute more than 5% are shown (assignment: H = HOMO, L = LUMO, L+1 = LUMO+1, H-1 = HOMO-1, etc.). 598 nm 594 nm H L (94%) H-2 L+1 (5%) 590 nm H L+1 (88%) H-1 L (7%) H-3 L (5%) H L (92%) H-3 L+1 (8%)

31 Table S7. Electron density difference plots of electron transitions (isovalue: e au -3 ) for M{Pc[N(C 4 H 9 ) 2 ] 8 } (M = 2H, Zn). Electron densities move from the cyan area to the purple area. Excited states with less than cm -1 and configurations which contribute more than 5% are shown (assignment: H = HOMO, L = LUMO, L+1 = LUMO+1, H-1 = HOMO-1, etc.). Q band nm 689 nm 678 nm 498 nm 478 nm H L (83%) H L+1 (60%) H-6 L (99%) H-6 L+1 (97%) H-1 L+1 (7%) H-3 L+1 (7%) H-1 L (26%) H-3 L (10%) 684 nm 684 nm 592 nm 592 nm 485 nm 485 nm H L (79%) H-2 L+1 (16%) H-2 L+1 (79%) H L (16%) H-2 L (79%) H L+1 (16%) H-2 L+1 (79%) H L (16%) H-5 L (98%) H-5 L+1 (98%)

32 Table S8. Electron density difference plots of electron transitions (isovalue: e au -3 ) for M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Zn). Electron densities move from the cyan area to the purple area. Excited states with less than cm -1 and configurations which contribute more than 5% are shown (assignment: H = HOMO, L = LUMO, L+1 = LUMO+1, H-1 = HOMO-1, etc.). Q band nm 718 nm 681 nm 574 nm 546 nm 472 nm 462 nm H L (82%) H L+1 (10%) H L+1 (82%) H L (11%) H-1 L+1 (95%) H-2 L+1 (83%) H-4 L (8%) H-3 L (5%) H-4 L (69%) H-4 L+1 (13%) H-5 L (5%) H-2 L+1 (5%) 701 nm 695 nm 571 nm 523 nm 460 nm H-4 L+1 (75%) H-4 L (13%) H-5 L (5%) H L (94%) H L+1 (89%) H-1 L+1 (77%) H-3 L (48%) H-4 L (79%) H L (5%) H-2 L (20%) H-2 L+1 (39%) H-3 L+1 (11%) H L+1 (5%)

33 Q band nm 729 nm 672 nm 540 nm 477 nm 468 nm H L (84%) H-3 L (8%) H L+1 (86%) H L (9%) H-2 L+1 (82%) H-4 L (16%) H-4 L (69%) H-4 L+1 (11%) H-2 L+1 (10%) H-4 L+1 (76%) H-4 L (9%) H-5 L (7%) 704 nm 690 nm 592 nm 555 nm 472 nm 462 nm H L (68%) H L+1 (26%) H L+1 (64%) H L (28%) H-2 L (97%) H-2 L+1 (92%) H-4 L (64%) H-4 L+1 (21%) H-4 L+1 (67%) H-4 L (22%) H-5 L (8%) 708 nm 679 nm 553 nm 539 nm 522 nm 468 nm H L (92%) H L+1 (94%) H-2 L (29%) H-1 L+1 (55%) H-3 L+1 (88%) H-4 L (81%) H-3 L (24%) H-2 L+1 (35%) H-4 L (6%) H-3 L+1 (5%) H-1 L+1 (23%) H-6 L+1 (5%) H-2 L+1 (15%)

34 Q band nm 697 nm 695 nm 541 nm 535 nm 521 nm 456 nm 453 nm H L (93%) H L+1 (94%) H-2 L (91%) H-1 L (56%) H-3 L+1 (84%) H-4 L+1 (88%) H-4 L (85%) H-3 L (35%) H-4 L (8%) H-6 L (6%) H-3 L+1 (6%) H-2 L (6%) H-6 L+1 (6%) 727 nm 664 nm 530 nm 475 nm H L (92%) H L+1 (95%) H-2 L+1 (79%) H-4 L (76%) H-4 L (19%) H-2 L+1 (16%) 682 nm 682 nm 559 nm 559 nm 468 nm 468 nm H L (50%) H L+1 (50%) H-1 L+1 (92%) H-1 L (92%) H-4 L (89%) H-4 L+1 (89%) H L+1 (43%) H L (43%) H-1 L (6%) H-1 L+1 (6%) H-6 L+1 (6%) H-6 L (6%)

35 Table S9. The molecular orbital maps (isovalue: e au -3 ) with their energy levels for MPc, M{Pc[N(C 4 H 9 ) 2 ] 8 }, and M{Pc[N(C 4 H 9 ) 2 ] 4 } (M = 2H, Zn). (assignment: H = HOMO, L = LUMO, L+1 = LUMO+1, H-1 = HOMO-1, etc.). L+1 L H H-1 H-2 H-3 H ev ev ev ev ev ev ev ev ev ev ev ev Ev ev ev ev ev ev ev ev ev ev

36 -2.32 ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev

37 -2.37 ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev ev

38 -2.37 ev ev ev ev ev ev ev