Molecular Engineering of Intensely Near-Infrared Absorbing Excited States in Highly Conjugated Oligo(porphinato)zinc−(Polypyridyl)metal(II) Supermolecules

Duncan, Timothy V.; Ishizuka, Tomoya; Therien, Michael J.

doi:10.1021/ja0707512

Molecular Engineering of Intensely Near-Infrared Absorbing Excited States in Highly Conjugated Oligo(porphinato)zinc−(Polypyridyl)metal(II) Supermolecules

Journal Article · Fri Jul 13 04:00:00 EDT 2007 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/ja0707512· OSTI ID:1036117

Duncan, Timothy V. ^[1]; Ishizuka, Tomoya ^[2]; Therien, Michael J. ^[2]

Univ. of Pennsylvania, Philadelphia, PA (United States); Duke University
Univ. of Pennsylvania, Philadelphia, PA (United States)

A new series of chromophores, MPZn_n, which combine ethyne-bridged bis(terpyridyl)metal(II)- (porphinato)zinc(II) (MPZn) and oligomeric, ethyne-bridged (porphinato)zinc(II) (PZn_n) architectures, have been synthesized and characterized, along with a series of derivatives bearing pyrrolidinyl electron-releasing groups on the ancillary terpyridine units (Pyr_mMPZn_n). Cyclic voltammetric studies, as well as NMR, electronic absorption, fluorescence, and femtosecond pump-probe transient absorption spectroscopies, have been employed to study the ground- and excited-state properties of these unusual chromophores. All of these species possess intensely absorbing excited states having large spectral bandwidth that penetrate deep in the near-infrared (NIR) energy regime. Electronic structural variation of the molecular framework shows that the excited-state absorption maximum can be extensively modulated [λmax(T₁ → T_n)] (880 nm < λmax < 1126 nm), while concomitantly maintaining impressively large T₁ → T_n absorption manifold spectral bandwidth (full width at half-maximum, fwhm, ~2000-2500 cm^-1). Furthermore, these studies enable correlation of supermolecular electronic structure with the magnitude of the excited-state lifetime (τ_es) and demonstrate that this parameter can be modulated over 4 orders of magnitude (~ns < τ_es < 45 μs). Terpyridyl pyrrolidinyl substituents can be utilized to destabilize terpyridyl ligand π* energy levels and diminish the E_1/2 (M^3+/2+) value of the bis(terpyridyl)metal(II) center: such perturbations determine the relative energies of the PZn_n-derived ¹π-π* and bis(terpyridyl)metal(II) charge-transfer states and establish whether the T₁-state wave functions of MPZn_n and Pyr_mMPZn_n species manifest the extensive electronic delocalization and charge-separated (CS) features characteristic of long-lived triplet states that absorb strongly in the NIR.

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:: 1036117

Report Number(s):: DOE-ER46156-2

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Journal Issue: 31 Vol. 129; ISSN 0002-7863

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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