Supporting Information

Rigidified and Expanded N-annulated Perylenes

as Efficient Donors in Organic Sensitizers for

Application in Solar Cells

Ping Li, Zhixiang Wang, and houyu Zhang*

State Key Laboratory of Supramolecular Structure and Materials,

Institute of Theoretical Chemistry, Jilin University, Changchun

130012, P. R. China

*E-mail:houyuzhang@jlu.edu.cn

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is © the Owner Societies 2019

Contents

Figure S1 Optimized structures of the dyes.

Figure S2 Optimized structures of dye-TiO2 complexes.

Figure S3 Spatial distributions of the frontier molecular orbitals

for the rest of dyes.

Figure S4 Computed difference in total density between the

ground and excited states (∆ρ) and graphical representation of

DCT for the B series of dyes.

Figure S5 Color-filled contours of localized orbital locator-π

(LOL-π) for two-sided rigidified NP moieties.

Table S1 Calculated HOMO energy levels of dyes A1, A2 and

A3 with different functionals in THF solution.

Table S2 Calculated maximum absorption wavelengths (max) of

dyes A1, A2, and A3 with different functionals.

Fig. S1 Optimized structures of dyes A3 and B3 and bilateral modified ones at the

level of PBE0/6-311G(d, p) in THF solution.

Fig. S2 Optimized structures of dye-TiO2 complexes at PBE0/6-311G(d, p)

(LANL2DZ for Ti atom) level in THF solution..

Fig. S3 Spatial distributions of the frontier molecular orbitals for the rest of dyes.

Fig. S4 Computed difference in total density between the ground and excited state (∆ρ)

and graphical representation of DCT with isocontour value of 0.0004 au for the B

series dyes.

Fig. S5 Color-filled contours of localized orbital locator-π (LOL-π) at a distance of

1.2 Bohr away from the molecular plane of the NP moieties, and the inserted values

indicate the NICS(1) values of the individual heterocyclic rings.

Table S1 Calculated HOMO energy levels of dyes A1, A2, and A3 in THF with

functionals of B3LYP, PBE0, and PBE38, and corresponding experimental values.

B3LYP

(20% HFexc)

PBE0

(25% HFexc)

PBE38

(37.5% HFexc)

Expt.

A1 -4.96 -5.16 -5.53 -5.10

A2 -4.79 -4.98 -5.33 -4.94

A3 -4.91 -5.11 -5.46 -4.94

Table S2 Calculated maximum absorption wavelengths (max) of dyes A1, A2, and A3

with functionals of PBE0, MPW1K, BHandHLYP, and CAM-B3LYP, and

corresponding experimental values. The values denote the percentage of nonlocal

Hartree-Fock exchange (HFexc) in parentheses.

PBE0

(25%)

PBE0-1/3

(33.3%)

MPW1K

(42.8%)

BHandHLYP

(50%)

CAM-B3LYP

(19% at SR and

65% at LR)

Expt.

A1 626 563 511 488 470 461

A2 699 634 578 552 528 560

A3 657 607 565 546 525 565