We design and synthesize a set of homologous organic molecules by taking advantage of facile and tailorable Suzuki cross coupling reactions to produce triarylbenzene derivatives. By adjusting the number and the arrangement of conjugated rings, the identity of heteroatoms, lengths of fluorinated alkyl chains, and other interaction parameters, we create a library of glassformers with a wide range of properties. Measurements of the glass transition temperature (Tg) show a power-law relationship between Tg and molecular weight (MW), with of the molecules, with an exponent of 0.3 ± 0.1, for Tg values spanning a range of 300–450 K. The trends in indices of refraction and expansion coefficients indicate a general increase in the glass density with MW, consistent with the trends observed in Tg variations. A notable exception to these trends was observed with the addition of alkyl and fluorinated alkyl groups, which significantly reduced Tg and increased the dynamical fragility (which is otherwise insensitive to MW). This is an indication of reduced density and increased packing frustrations in these systems, which is also corroborated by the observations of the decreasing index of refraction with increasing length of these groups. These data were used to launch a new database for glassforming materials, glass.apps.sas.upenn.edu.
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14 December 2021
Research Article|
December 10 2021
Design of a homologous series of molecular glassformers
Special Collection:
Slow Dynamics
Sarah E. Wolf
;
Sarah E. Wolf
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Tianyi Liu;
Tianyi Liu
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Shivajee Govind
;
Shivajee Govind
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Haoqiang Zhao;
Haoqiang Zhao
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Georgia Huang;
Georgia Huang
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Aixi Zhang;
Aixi Zhang
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Yu Wu;
Yu Wu
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Jocelyn Chin;
Jocelyn Chin
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Kevin Cheng;
Kevin Cheng
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Elmira Salami-Ranjbaran;
Elmira Salami-Ranjbaran
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Feng Gao;
Feng Gao
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Gui Gao;
Gui Gao
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Yi Jin
;
Yi Jin
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Youge Pu
;
Youge Pu
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Thiago Gomes Toledo;
Thiago Gomes Toledo
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Keyume Ablajan;
Keyume Ablajan
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Patrick J. Walsh
;
Patrick J. Walsh
a)
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Zahra Fakhraai
Zahra Fakhraai
a)
Department of Chemistry, University of Pennsylvania
, Philadelphia, Pennsylvania 19104, USA
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Note: This paper is part of the JCP Special Topic on Slow Dynamics.
J. Chem. Phys. 155, 224503 (2021)
Article history
Received:
August 10 2021
Accepted:
November 16 2021
Citation
Sarah E. Wolf, Tianyi Liu, Shivajee Govind, Haoqiang Zhao, Georgia Huang, Aixi Zhang, Yu Wu, Jocelyn Chin, Kevin Cheng, Elmira Salami-Ranjbaran, Feng Gao, Gui Gao, Yi Jin, Youge Pu, Thiago Gomes Toledo, Keyume Ablajan, Patrick J. Walsh, Zahra Fakhraai; Design of a homologous series of molecular glassformers. J. Chem. Phys. 14 December 2021; 155 (22): 224503. https://doi.org/10.1063/5.0066410
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