Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane

Gong, Xirui; Young, Ryan M.; Hartlieb, Karel J.; Miller, Claire; Wu, Yilei; Xiao, Hai; Li, Peng; Hafezi, Nema; Zhou, Jiawang; Ma, Lin; Cheng, Tao; Goddard, III, William A.; Farha, Omar K.; Hupp, Joseph T.; Wasielewski, Michael R.; Stoddart, J. Fraser

doi:10.1021/jacs.6b13223

Title: Intramolecular Energy and Electron Transfer within a Diazaperopyrenium-Based Cyclophane

Journal Article · Fri Mar 10 00:00:00 EST 2017 · Journal of the American Chemical Society

DOI:https://doi.org/10.1021/jacs.6b13223· OSTI ID:1346430

Gong, Xirui;

; Hartlieb, Karel J.; Miller, Claire; Wu, Yilei;

^[1];

; Hafezi, Nema;

; Ma, Lin;

^[1];

^[2];

;

Materials and Process Simulation Center, California Institute of Technology, Pasadena, California 91125, United States
Department of Chemistry, Faculty of Science, King Abdulaziz University, Jeddah 22254, Saudi Arabia

Molecules capable of performing highly efficient energy transfer and ultrafast photoinduced electron transfer in well-defined multichromophoric structures are indispensable to the development of artificial photofunctional systems. Herein, we report on the synthesis, characterization, and photophysical properties of a rationally designed multichromophoric tetracationic cyclophane, DAPPBox⁴⁺, containing a diazaperopyrenium (DAPP²⁺) unit and an extended viologen (ExBIPY²⁺) unit, which are linked together by two p-xylylene bridges. Both ¹H NMR spectroscopy and single-crystal X-ray diffraction analysis confirm the formation of an asymmetric, rigid, box-like cyclophane, DAPPBox⁴⁺. The solid-state superstructure of this cyclophane reveals a herringbone-type packing motif, leading to two types of π···π interactions: (i) between the ExBIPY²⁺ unit and the DAPP²⁺ unit (π···π distance of 3.7 Å) in the adjacent parallel cyclophane, as well as (ii) between the ExBIPY²⁺ unit (π···π distance of 3.2 Å) and phenylene ring in the closest orthogonal cyclophane. Moreover, the solution-phase photophysical properties of this cyclophane have been investigated by both steady-state and time-resolved absorption and emission spectroscopies. Upon photoexcitation of DAPPBox⁴⁺ at 330 nm, rapid and quantitative intramolecular energy transfer occurs from the ^1*ExBIPY²⁺ unit to the DAPP²⁺ unit in 0.5 ps to yield ^1*DAPP²⁺. As a result, the same excitation wavelength simultaneously populates a higher excited state of ^1*DAPP²⁺ which then undergoes ultrafast intramolecular electron transfer from ^1*DAPP²⁺ to ExBIPY²⁺ to yield the DAPP^3+•–ExBIPY^+• radical ion pair in τ = 1.5 ps. Selective excitation of DAPP²⁺ at 505 nm populates a lower excited state where electron transfer is kinetically unfavorable.

View Journal Article

Cite

Export

Save

Research Organization:: Northwestern Univ., Evanston, IL (United States); Argonne National Lab. (ANL), Argonne, IL (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: FG02 87ER13808; FG02-99ER14999

OSTI ID:: 1346430

Alternate ID(s):: OSTI ID: 1351622

Journal Information:: Journal of the American Chemical Society, Journal Name: Journal of the American Chemical Society Vol. 139 Journal Issue: 11; ISSN 0002-7863

Publisher:: American Chemical SocietyCopyright Statement

Country of Publication:: United States

Language:: English

Citation Metrics:

Cited by: 32 works

Citation information provided by
Web of Science

Cited By (8)

CCDC 1480961: Experimental Crystal Structure Determination: TAVLOU : 9,16,39,46-tetra-azoniatridecacyclo[44.2.2.22,5.26,9.211,14.241,44.116,24.131,39.018,23.021,34.022,27.028,33.032,37]hexaconta-1(48),2,4,6,8,11,13,16(54),17,19,21,23,25,27,29,31(53),32(37),33,35,38,41,43,46,49,51,55,57,59-octacosaene tetrakis(trifluoroacetate) unknown solvate Space Group: P 1 (2), Cell: a 13.3141(7)Å b 21.1146(10)Å c 23.4964(13)Å, α 96.654(4)° β 99.661(4)° γ 105.932(4)° Gong, Xirui; Young, Ryan M.; Hartlieb, Karel J. The Cambridge Crystallographic Data Centre, vp https://doi.org/10.5517/ccdc.csd.cc1lq1y9	dataset	May 2016
Heli(aza)cene: A Helical Molecular Tweezer with Tunable Intra- and Intermolecular Charge Transfer Kumar, Rajesh; Semwal, Shrivats; Choudhury, Joyanta Chemistry - A European Journal, Vol. 23, Issue 60 https://doi.org/10.1002/chem.201703781	journal	October 2017
Versatile and Switchable Responsive Properties of a Lanthanide‐Viologen Metal–Organic Framework Gong, Teng; Sui, Qi; Li, Peng Small, Vol. 15, Issue 5 https://doi.org/10.1002/smll.201803468	journal	January 2019
Choosing sides: unusual ultrafast charge transfer pathways in an asymmetric electron-accepting cyclophane that binds an electron donor Zhou, Jiawang; Wu, Yilei; Roy, Indranil Chemical Science, Vol. 10, Issue 15 https://doi.org/10.1039/c8sc05514a	journal	January 2019
Guest recognition enhanced by lateral interactions Jiao, Tianyu; Cai, Kang; Liu, Zhichang Chemical Science, Vol. 10, Issue 19 https://doi.org/10.1039/c9sc00591a	journal	January 2019
Boosting the electron mobilities of dimeric perylenediimides by simultaneously enhancing intermolecular and intramolecular electronic interactions Guo, Yuan; Han, Guangchao; Duan, Ruihong Journal of Materials Chemistry A, Vol. 6, Issue 29 https://doi.org/10.1039/c8ta04932g	journal	January 2018
Tunable low-dimensional self-assembly of H-shaped bichromophoric perylenediimide Gemini in solution Huang, Yinjuan; Yu, Fei; Cao, Xun Nanoscale, Vol. 12, Issue 5 https://doi.org/10.1039/c9nr10607c	journal	January 2020
Through-Space Conjugation: A Thriving Alternative for Optoelectronic Materials Li, Jinshi; Shen, Pingchuan; Zhao, Zujin CCS Chemistry, Vol. 1, Issue 2 https://doi.org/10.31635/ccschem.019.20180020	journal	January 2019