Linear and nonlinear optical properties of a macrocyclic trichromophore bundle with parallel-aligned dipole moments.
A macrocyclic trichromophore bundle 1 with parallel-aligned dipole moments has been synthesized to study the influence of aggregation and orientation of a nonlinear optical (NLO) chromophore on its optical properties. The linear and nonlinear optical properties of 1 and a single chromophore standard 2 have been studied by UV-vis absorption, fluorescence, solvatochromic spectrometry, and hyper-Rayleigh scattering (HRS). Reduced first-order hyperpolarizability beta, hypsochromic shift, enhanced solvatochromic shifts, and fluorescence quenching for individual chromophores were observed when 1 was compared with 2. Analysis of the data showed that the transition dipole moment changes only slightly when the chromophores are parallel aligned in the bundle architecture. However, the apparent hyperpolarizability of the individual chromophores decreased significantly by about 20%. The reduction in beta for the individual chromophores in 1 is largely due to the hypsochromic shift, i.e., excitation energy increase of the interband (charge-transfer) energy gap and the reduced difference between the ground-state and excited-state dipole moments. The hypsochromic shift and fluorescence quenching are consistent with exciton theory. Possible reasons for the enhanced solvatochromic shift are discussed.
Department of Chemistry, University of Washington, Seattle, Washington 98195, USA. liaoyi@u.washington.edu
Yi
Y
Liao
Kimberly A
KA
Firestone
Sanchali
S
Bhattacharjee
Jingdong
J
Luo
Marnie
M
Haller
Steven
S
Hau
Cyrus A
CA
Anderson
David
D
Lao
Bruce E
BE
Eichinger
Bruce H
BH
Robinson
Philip J
PJ
Reid
Alex K-Y
AK
Jen
Larry R
LR
Dalton