title: Ultra-High-Response, Multiply Twisted Electro-optic Chromophores: Influence of π-System Elongation and Interplanar Torsion on Hyperpolarizability.
abstract: The systematic synthesis, structural, optical spectroscopic, and second-order nonlinear optical (NLO) characterization of a series of donor-acceptor poly-arylene chromophores which have heretofore unachieved π-extension and substantial twisting from planarity, are reported: specifically, two-ring 2TTMC, dicyano(4-(3,5-dimethyl-1-(2-propylheptyl)pyridin-1-ium-4-yl)-3-methylphenyl)methanide; three-ring 3TTMC, dicyano(4'-(3,5-dimethyl-1-(2-propylheptyl)pyridin-1-ium-4-yl)-2,2',3',5',6'-pentamethyl[1,1'-biphenyl]-4-yl)methanide; and four-ring 4TTMC, dicyano(4″-(3,5-dimethyl-1-(2-propylheptyl)pyridin-1-ium-4-yl)-2,2',3″,6,6'-pentamethyl[1,1':4',1″-terphenyl]-4-yl)methanide. Single-crystal X-ray diffraction, DFT-optimized geometries, and B3LYP/INDO-SOS analysis identify three key features underlying the very large NLO response: (1) For ring catenation of three or greater, sterically enforced π-system twists are only essential near the chromophore donor and acceptor sites to ensure large NLO responses. (2) For synthetic efficiency, deletion of one ortho-methyl group from o,o',o″,o‴-tetramethylbiaryl junctures, only slightly relaxes the biaryl twist angle from 89.6° to ∼80°. (3) Increased arylene catenation from two to three to four rings (2TTMC→ 3TTMC → 4TTMC) greatly enhances NLO response, zwitterionic charge localization, and thus the ground-state dipole moment, consistent with the contracted antiparallel solid-state π-π stacking distances of 8.665 → 7.883 → 7.361 Å, respectively. This supports zwitterionic ground states in these chromophores as do significant optical spectroscopic solvatochromic shifts, with aryl-aryl twisting turning on significant intra-subfragment absorption. Computed molecular hyperpolarizabilities (μβ) approach an unprecedented 900,000 × 10(-48) esu, while estimated chromophore figures of merit, μβ(vec)/M(w), approach 1500 × 10(-48) esu, 1.5 times larger than the highest known values for twisted chromophores and >33 times larger than that of planar donor-acceptor chromophores.
authors.affiliation: Department of Chemistry and the Materials Research Center, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors.forename: Yanrong
authors.initials: Y
authors.lastname: Shi
authors.affiliation: Department of Chemistry and the Materials Research Center, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors.forename: David
authors.initials: D
authors.lastname: Frattarelli
authors.affiliation: Department of Chemistry and the Materials Research Center, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors.forename: Naoki
authors.initials: N
authors.lastname: Watanabe
authors.affiliation: Department of Chemistry and the Materials Research Center, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors.forename: Antonio
authors.initials: A
authors.lastname: Facchetti
authors.affiliation: Dipartimento di Chimica dell' Università di Milano and Unità di Ricerca dell'INSTM di Milano, Via Golgi 19, I-20133 Milano, Italy.
authors.forename: Elena
authors.initials: E
authors.lastname: Cariati
authors.affiliation: Dipartimento di Chimica dell' Università di Milano and Unità di Ricerca dell'INSTM di Milano, Via Golgi 19, I-20133 Milano, Italy.
authors.forename: Stefania
authors.initials: S
authors.lastname: Righetto
authors.affiliation: Dipartimento di Chimica dell' Università di Milano and Unità di Ricerca dell'INSTM di Milano, Via Golgi 19, I-20133 Milano, Italy.
authors.forename: Elisa
authors.initials: E
authors.lastname: Tordin
authors.affiliation: Dipartimento di Chimica, Biologia e Biotecnologie and CIRCC, Università degli Studi di Perugia , Via Elce di Sotto, I-06123 Perugia, Italy.
authors.forename: Cristiano
authors.initials: C
authors.lastname: Zuccaccia
authors.affiliation: Dipartimento di Chimica, Biologia e Biotecnologie and CIRCC, Università degli Studi di Perugia , Via Elce di Sotto, I-06123 Perugia, Italy.
authors.forename: Alceo
authors.initials: A
authors.lastname: Macchioni
authors.affiliation: Department of Chemistry and the Materials Research Center, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors.forename: Staci L
authors.initials: SL
authors.lastname: Wegener
authors.affiliation: Department of Chemistry and the Materials Research Center, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors.forename: Charlotte L
authors.initials: CL
authors.lastname: Stern
authors.affiliation: Department of Chemistry and the Materials Research Center, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors.forename: Mark A
authors.initials: MA
authors.lastname: Ratner
authors.affiliation: Department of Chemistry and the Materials Research Center, Northwestern University , 2145 Sheridan Road, Evanston, Illinois 60208-3113, United States.
authors.forename: Tobin J
authors.initials: TJ
authors.lastname: Marks