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Peer-reviewedCC BY 4.0Inorganic Chemistry

Fluorinated Arylethynyl Substituents in Zn(II) Complexes of Azadipyrromethene Guide Self-Assembly in Crystals

  • David A. Raufman1
  • Neha Jadhav1
  • Shashika A. Arachchige1
  • Lexi R. Knight1
  • Jayvic C. Jimenez2
  • Geneviève Sauvé1
  1. 1Department of Chemistry, Case Western Reserve University, 10900 Euclid Avenue, Cleveland, Ohio 44106, United States
  2. 2Lawrence Livermore National Laboratory, Livermore, California 94550, United States
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Abstract

Zn­(II) complexes of 2,8-arylethynyl 1,3,7,9-tetraphenyl azadipyrromethenes are promising molecular semiconductors with strong visible-NIR absorption and a nonplanar distorted tetrahedral geometry around the Zn­(II) center, but their charge transport properties are limited by the orientation and strength of intermolecular π–π stacking interactions. To optimize their intermolecular π–π stacking interactions, we explored substitution of the pyrrolic phenylethynyl groups in Zn­(L1)2 at the phenyl meta positions with either fluorines (Zn­(L1-m-2F)2) or trifluoromethyls (Zn­(L1-m-2CF3)2). Fluorination had minimal effects on optical properties and slightly deepened frontier orbital energy levels. On the other hand, fluorination strongly affected the complexes’ molecular packing: while Zn­(L1-m-2F)2 had the same C2/c space group as Zn­(L1)2, the −CF3 groups in Zn­(L1-m-2CF3)2 promoted a higher ordered space group of Fddd. Further, in Zn­(L1)2 and Zn­(L1-m-2F)2, the phenylethynyl groups stack with the core phenyls of neighboring molecules, whereas in Zn­(L1-m-2CF3)2, the bis­(trifluoromethyl)-substituted phenylethynyl groups of neighboring molecules stack with each other with a shorter π–π stacking distance than in the other two molecules. Computations revealed that fluorination decreases the internal reorganization energy for electron transfer and increases overlap integrals for charge transfer. Fluorination is thus a promising strategy to tune molecular packing and parameters relevant to charge transport.

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Cite

BibTeXRIS
BibTeX
@article{raufman2026fluorinated,
  title = {{Fluorinated Arylethynyl Substituents in Zn(II) Complexes of Azadipyrromethene Guide Self-Assembly in Crystals}},
  author = {David A. Raufman and Neha Jadhav and Shashika A. Arachchige and Lexi R. Knight and Jayvic C. Jimenez and Geneviève Sauvé},
  journal = {Inorganic Chemistry},
  year = {2026},
  month = oct,
  doi = {10.1021/acs.inorgchem.6c03689},
  url = {https://doi.org/10.1021/acs.inorgchem.6c03689},
  note = {CC BY 4.0},
}
RIS
TY  - JOUR
TI  - Fluorinated Arylethynyl Substituents in Zn(II) Complexes of Azadipyrromethene Guide Self-Assembly in Crystals
AU  - David A. Raufman
AU  - Neha Jadhav
AU  - Shashika A. Arachchige
AU  - Lexi R. Knight
AU  - Jayvic C. Jimenez
AU  - Geneviève Sauvé
PY  - 2026
DA  - 2026/10/15
JO  - Inorganic Chemistry
DO  - 10.1021/acs.inorgchem.6c03689
UR  - https://doi.org/10.1021/acs.inorgchem.6c03689
AB  - Zn­(II) complexes of 2,8-arylethynyl 1,3,7,9-tetraphenyl azadipyrromethenes are promising molecular semiconductors with strong visible-NIR absorption and a nonplanar distorted tetrahedral geometry around the Zn­(II) center, but their charge transport properties are limited by the orientation and strength of intermolecular π–π stacking interactions. To optimize their intermolecular π–π stacking interactions, we explored substitution of the pyrrolic phenylethynyl groups in Zn­(L1)2 at the phenyl meta positions with either fluorines (Zn­(L1-m-2F)2) or trifluoromethyls (Zn­(L1-m-2CF3)2). Fluorination had minimal effects on optical properties and slightly deepened frontier orbital energy levels. On the other hand, fluorination strongly affected the complexes’ molecular packing: while Zn­(L1-m-2F)2 had the same C2/c space group as Zn­(L1)2, the −CF3 groups in Zn­(L1-m-2CF3)2 promoted a higher ordered space group of Fddd. Further, in Zn­(L1)2 and Zn­(L1-m-2F)2, the phenylethynyl groups stack with the core phenyls of neighboring molecules, whereas in Zn­(L1-m-2CF3)2, the bis­(trifluoromethyl)-substituted phenylethynyl groups of neighboring molecules stack with each other with a shorter π–π stacking distance than in the other two molecules. Computations revealed that fluorination decreases the internal reorganization energy for electron transfer and increases overlap integrals for charge transfer. Fluorination is thus a promising strategy to tune molecular packing and parameters relevant to charge transport.
SN  - 0020-1669
SN  - 1520-510X
ER  -