Essential States Model for Merocyanine Dye Stacks: Bridging Electronic and Optical Absorption Properties

被引:26
作者
Bialas, David [1 ]
Zhong, Chuwei [1 ]
Wuerthner, F. [2 ,3 ]
Spano, Frank C. [1 ]
机构
[1] Temple Univ, Dept Chem, 130 Beury Hall,1901 N 13th St, Philadelphia, PA 19122 USA
[2] Univ Wurzburg, Inst Organ Chem, D-97074 Wurzburg, Germany
[3] Univ Wurzburg, Ctr Nanosyst Chem, Theodor Boveri Weg, D-97074 Wurzburg, Germany
基金
美国国家科学基金会;
关键词
BOND-LENGTH ALTERNATION; VIBRATIONAL FINE-STRUCTURE; ORGANIC SEMICONDUCTORS; MOLECULAR-STRUCTURE; SYMMETRY-BREAKING; CYANINE LIMIT; DESIGN; AGGREGATION; CHROMOPHORES; POLYMETHINE;
D O I
10.1021/acs.jpcc.9b04430
中图分类号
O64 [物理化学(理论化学)、化学物理学];
学科分类号
070304 ; 081704 ;
摘要
An extension of the essential states model is developed to investigate the absorption and electronic properties of a highly dipolar merocyanine dye and double and quadruple pi-stacks formed upon the folding and self-assembly of appropriate spacer-tethered bis(merocyanine) dyes. Our analysis reveals that a simple two-state model is not sufficient to adequately describe the absorption features of a single chromophore. However, by including an additional bridge state, the absorption features are well described and reasonable values for the permanent and transition dipole moments are obtained. We show that the low-energy absorption band of the folded double stack results from vibronic coupling, whereas the additional absorption shoulder observed in the spectrum of the self-assembled quadruple stack is due to a transition to a lower excited state. Furthermore, the chromophores within both pi-stacks exhibit an increase in the charge-transfer character in the ground state with respect to the single chromophore arising from polarizability effects, which are not accounted for in the conventional Frenkel exciton theory. These insights are of significant importance for the proper design of functional materials based on merocyanines and dipolar chromophores in general.
引用
收藏
页码:18654 / 18664
页数:11
相关论文
共 84 条
  • [1] Rational design of molecules with large hyperpolarizabilities. Electric field, solvent polarity, and bond length alternation effects on merocyanine dye linear and nonlinear optical properties
    Albert, IDL
    Marks, TJ
    Ratner, MA
    [J]. JOURNAL OF PHYSICAL CHEMISTRY, 1996, 100 (23) : 9714 - 9725
  • [2] [Anonymous], 1964, SOV PHYS-USP, DOI DOI 10.1070/PU1964V007N02ABEH003659
  • [3] Influence of Solid-State Packing of Dipolar Merocyanine Dyes on Transistor and Solar Cell Performances
    Arjona-Esteban, Alhama
    Krumrain, Julian
    Liess, Andreas
    Stolte, Matthias
    Huang, Lizhen
    Schmidt, David
    Stepanenko, Vladimir
    Gsaenger, Marcel
    Hertel, Dirk
    Meerholz, Klaus
    Wuerthner, Frank
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2015, 137 (42) : 13524 - 13534
  • [4] Photochemical conversion of solar energy
    Balzani, Vincenzo
    Credi, Alberto
    Venturi, Margherita
    [J]. CHEMSUSCHEM, 2008, 1 (1-2) : 26 - 58
  • [5] Spectroscopic Investigation and Theoretical Modeling of Benzothiadiazole-Based Charge-Transfer Chromophores: From Solution to Nanoaggregates
    Bardi, Brunella
    Dall'Agnese, Chunxiang
    Ching, Kathleen I. Moineau-Chane
    Painelli, Anna
    Terenziani, Francesca
    [J]. JOURNAL OF PHYSICAL CHEMISTRY C, 2017, 121 (32) : 17466 - 17478
  • [6] π-Conjugated Zwitterions as Paradigm of Donor-Acceptor Building Blocks in Organic-Based Materials
    Beverina, Luca
    Pagani, Giorgio A.
    [J]. ACCOUNTS OF CHEMICAL RESEARCH, 2014, 47 (02) : 319 - 329
  • [7] Structural and quantum chemical analysis of exciton coupling in homo- and heteroaggregate stacks of merocyanines
    Bialas, David
    Zitzler-Kunkel, Andre
    Kirchner, Eva
    Schmidt, David
    Wuerthner, Frank
    [J]. NATURE COMMUNICATIONS, 2016, 7
  • [8] Folding-induced exciton coupling in homo- and heterodimers of merocyanine dyes
    Bialas, David
    Kirchner, Eva
    Wuerthner, Frank
    [J]. CHEMICAL COMMUNICATIONS, 2016, 52 (19) : 3777 - 3780
  • [9] Large quadratic hyperpolarizabilities with donor-acceptor polyenes exhibiting optimum bond length alternation: Correlation between structure and hyperpolarizability
    BlanchardDesce, M
    Alain, V
    Bedworth, PV
    Marder, SR
    Fort, A
    Runser, C
    Barzoukas, M
    Lebus, S
    Wortmann, R
    [J]. CHEMISTRY-A EUROPEAN JOURNAL, 1997, 3 (07) : 1091 - 1104
  • [10] Continuous Symmetry Breaking Induced by Ion Pairing Effect in Heptamethine Cyanine Dyes: Beyond the Cyanine Limit
    Bouit, Pierre-Antoine
    Aronica, Christophe
    Toupet, Loic
    Le Guennic, Boris
    Andraud, Chantal
    Maury, Olivier
    [J]. JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (12) : 4328 - 4335