The Roles of Molecular Structure and Effective Optical Symmetry in Evolving Dipolar Chromophoric Building Blocks to Potent Octopolar Nonlinear Optical Chromophores

Ishizuka, Tomoya; Sinks, Louise E.; Song, Kai; Hung, Sheng-Ting; Nayak, Animesh; Clays, Koen; Therien, Michael J.

doi:10.1021/ja105004k

The Roles of Molecular Structure and Effective Optical Symmetry in Evolving Dipolar Chromophoric Building Blocks to Potent Octopolar Nonlinear Optical Chromophores

Journal Article · Tue Feb 15 04:00:00 EST 2011 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja105004k· OSTI ID:1036222

Ishizuka, Tomoya ^[1]; Sinks, Louise E. ^[2]; Song, Kai ^[3]; Hung, Sheng-Ting ^[4]; Nayak, Animesh ^[5]; Clays, Koen ^[4]; Therien, Michael J. ^[6]

Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States; Duke University
Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States
Beijing National Laboratory for Molecular Sciences, Key Laboratory of Photochemistry, Institute of Chemistry, Chinese Academy of Sciences, Beijing 100190, China
Department of Chemistry, University of Leuven, B-3001 Leuven, Belgium
Department of Chemistry, University of Pennsylvania, 231 South 34th Street, Philadelphia, Pennsylvania 19104-6323, United States; Department of Chemistry, French Family Science Center, 124 Science Drive, Duke University, Durham, North Carolina 27708-0346, United States
Department of Chemistry, French Family Science Center, 124 Science Drive, Duke University, Durham, North Carolina 27708-0346, United States

A series of mono-, bis-, tris-, and tetrakis(porphinato)zinc(II) (PZn)-elaborated ruthenium(II) bis(terpyridine) (Ru) complexes have been synthesized in which an ethyne unit connects the macrocycle meso carbon atom to terpyridyl (tpy) 4-, 4²-, and 4²-positions. These supermolecular chromophores, based on the ruthenium(II) [5-(4²-ethynyl-(2,2²;6²,2²-terpyridinyl))-10,20-bis(2²,6²-bis(3,3-dimethyl-1-butyloxy)phenyl)porphinato]zinc(II)-(2,2²;6²,2²-terpyridine)2+ bis-hexafluorophosphate (RuPZn) archetype, evince strong mixing of the PZn-based oscillator strength with ruthenium terpyridyl charge resonance bands. Potentiometric and linear absorption spectroscopic data indicate that for structures in which multiple PZn moieties are linked via ethynes to a [Ru(tpy)2]2+ core, little electronic coupling is manifest between PZn units, regardless of whether they are located on the same or opposite tpy ligand. Congruent with these experiments, pump probe transient absorption studies suggest that the individual RuPZn fragments of these structures exhibit, at best, only modest excited-state electronic interactions that derive from factors other than the dipole dipole interactions of these strong oscillators; this approximate independent character of the component RuPZn oscillators enables fabrication of nonlinear optical (NLO) multipoles with extraordinary hyperpolarizabilities. Dynamic hyperpolarizability (Î²Î») values and depolarization ratios (Ï) were determined from hyper-Rayleigh light scattering (HRS) measurements carried out at an incident irradiation wavelength (Î»inc) of 1300 nm. The depolarization ratio data provide an experimental measure of chromophore optical symmetry; appropriate coupling of multiple charge-transfer oscillators produces structures having enormous averaged hyperpolarizabilities (Î²HRS values), while evolving the effective chromophore symmetry from purely dipolar (e.g., Ru(tpy)[4-(Zn-porphyrin)ethynyl-tpy](PF6)2, Î²HRS = 1280 10-30 esu, Ï = 3.8; Ru(tpy)[4²-(Zn-porphyrin)ethynyl-tpy](PF6)2, Î²HRS = 2100 10-30 esu, Ï = 3.8) to octopolar (e.g., Ru[4,4²-bis(Zn-porphyrin)ethynyl-tpy]2(PF6)2, Î²HRS = 1040 10-30 esu, Ï = 1.46) via structural motifs that possess intermediate values of the depolarization ratio. The chromophore design roadmap provided herein gives rise to octopolar supermolecules that feature by far the largest off-diagonal octopolar first hyperpolarizability tensor components ever reported, with the effectively octopolar Ru[4,4²-bis(Zn-porphyrin)ethynyl-tpy]2(PF6)2 possessing a Î²HRS value at 1300 nm more than a factor of 3 larger than that determined for any chromophore having octopolar symmetry examined to date. Because NLO octopoles possess omnidirectional NLO responses while circumventing the electrostatic interactions that drive bulk-phase centrosymmetry for NLO dipoles at high chromophore concentrations, the advent of octopolar NLO chromophores having vastly superior Î²HRS values at technologically important wavelengths will motivate new experimental approaches to achieve acentric order in both bulk-phase and thin film structures.

Research Organization:: Univ. of Pennsylvania, Philadelphia, PA (United States)

Sponsoring Organization:: USDOE SC Office of Basic Energy Sciences (SC-22)

DOE Contract Number:: FG02-04ER46156

OSTI ID:: 1036222

Report Number(s):: DOE-ER46156-17

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 9 Vol. 133; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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