Novel triplet germylenes in focus: normal vs. abnormal triplet exocyclic tetrazol-5-vinylidene germylenes at DFT

Samaneh Ashenagar; Mohamad Zaman Kassaee; Peter T. Cummings

doi:10.1007/s00894-019-4213-2

Novel triplet germylenes in focus: normal vs. abnormal triplet exocyclic tetrazol-5-vinylidene germylenes at DFT

Samaneh Ashenagar, Mohamad Zaman Kassaee^*, Peter T. Cummings

^*Corresponding author for this work

Research output: Contribution to journal › Article › peer-review

1 Citation (Scopus)

Abstract

Substituent effects on stability (assumed as the singlet and triplet energy gaps, ΔΕ_S-T) of novel 1,4-disubstituted-tetrazole-5-vinylidene germylenes (normal, 1_R) and their corresponding 1,3-disubstituted-tetrazole-5-vinylidene germylenes (abnormal, 2_R) are computed and compared, at B3LYP/6-311++G** and M06/6-311++G**, where R = H, CN, CF₃, F, SH, C₆H₆, OMe, and OH. Interestingly, every triplet vinylidene germylene shows more stability than its corresponding singlet. Also, every triplet abnormal isomer (2_R) emerges to be more stable than its corresponding normal (1_R). All abnormal 2_R isomers show broader band gaps (ΔE_HOMO–LUMO) and higher nucleophilicity (N), but less electrophilicity (ω) than their corresponding normal 1_R isomers. The NICS (nuclear-independent chemical shift) results indicate that every 1_R (except singlet 2_Ph) emerges more aromatic than its corresponding 2_R. Our Hammet studies indicate that 1_R is more sensitive to the electronic effects of substituents, R, than 2_R. Electron-donating species increase N in both 1_R and 2_R, while electron-withdrawing groups increase stability.

Original language	English
Article number	371
Journal	Journal of Molecular Modeling
Volume	25
DOIs	https://doi.org/10.1007/s00894-019-4213-2
Publication status	Published - 2 Dec 2019

Keywords

Band gap
Electronic effect
Singlet-triplet energy gap
Tetrazole-vinylidene germylene
Triplet state

ASJC Scopus subject areas

Catalysis
Computer Science Applications
Physical and Theoretical Chemistry
Organic Chemistry
Inorganic Chemistry
Computational Theory and Mathematics

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title = "Novel triplet germylenes in focus: normal vs. abnormal triplet exocyclic tetrazol-5-vinylidene germylenes at DFT",

abstract = "Substituent effects on stability (assumed as the singlet and triplet energy gaps, ΔΕS-T) of novel 1,4-disubstituted-tetrazole-5-vinylidene germylenes (normal, 1R) and their corresponding 1,3-disubstituted-tetrazole-5-vinylidene germylenes (abnormal, 2R) are computed and compared, at B3LYP/6-311++G** and M06/6-311++G**, where R = H, CN, CF3, F, SH, C6H6, OMe, and OH. Interestingly, every triplet vinylidene germylene shows more stability than its corresponding singlet. Also, every triplet abnormal isomer (2R) emerges to be more stable than its corresponding normal (1R). All abnormal 2R isomers show broader band gaps (ΔEHOMO–LUMO) and higher nucleophilicity (N), but less electrophilicity (ω) than their corresponding normal 1R isomers. The NICS (nuclear-independent chemical shift) results indicate that every 1R (except singlet 2Ph) emerges more aromatic than its corresponding 2R. Our Hammet studies indicate that 1R is more sensitive to the electronic effects of substituents, R, than 2R. Electron-donating species increase N in both 1R and 2R, while electron-withdrawing groups increase stability.",

keywords = "Band gap, Electronic effect, Singlet-triplet energy gap, Tetrazole-vinylidene germylene, Triplet state",

author = "Samaneh Ashenagar and Kassaee, \{Mohamad Zaman\} and Cummings, \{Peter T.\}",

note = "Publisher Copyright: {\textcopyright} 2019, Springer-Verlag GmbH Germany, part of Springer Nature.",

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AU - Ashenagar, Samaneh

AU - Kassaee, Mohamad Zaman

AU - Cummings, Peter T.

PY - 2019/12/2

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N2 - Substituent effects on stability (assumed as the singlet and triplet energy gaps, ΔΕS-T) of novel 1,4-disubstituted-tetrazole-5-vinylidene germylenes (normal, 1R) and their corresponding 1,3-disubstituted-tetrazole-5-vinylidene germylenes (abnormal, 2R) are computed and compared, at B3LYP/6-311++G** and M06/6-311++G**, where R = H, CN, CF3, F, SH, C6H6, OMe, and OH. Interestingly, every triplet vinylidene germylene shows more stability than its corresponding singlet. Also, every triplet abnormal isomer (2R) emerges to be more stable than its corresponding normal (1R). All abnormal 2R isomers show broader band gaps (ΔEHOMO–LUMO) and higher nucleophilicity (N), but less electrophilicity (ω) than their corresponding normal 1R isomers. The NICS (nuclear-independent chemical shift) results indicate that every 1R (except singlet 2Ph) emerges more aromatic than its corresponding 2R. Our Hammet studies indicate that 1R is more sensitive to the electronic effects of substituents, R, than 2R. Electron-donating species increase N in both 1R and 2R, while electron-withdrawing groups increase stability.

AB - Substituent effects on stability (assumed as the singlet and triplet energy gaps, ΔΕS-T) of novel 1,4-disubstituted-tetrazole-5-vinylidene germylenes (normal, 1R) and their corresponding 1,3-disubstituted-tetrazole-5-vinylidene germylenes (abnormal, 2R) are computed and compared, at B3LYP/6-311++G** and M06/6-311++G**, where R = H, CN, CF3, F, SH, C6H6, OMe, and OH. Interestingly, every triplet vinylidene germylene shows more stability than its corresponding singlet. Also, every triplet abnormal isomer (2R) emerges to be more stable than its corresponding normal (1R). All abnormal 2R isomers show broader band gaps (ΔEHOMO–LUMO) and higher nucleophilicity (N), but less electrophilicity (ω) than their corresponding normal 1R isomers. The NICS (nuclear-independent chemical shift) results indicate that every 1R (except singlet 2Ph) emerges more aromatic than its corresponding 2R. Our Hammet studies indicate that 1R is more sensitive to the electronic effects of substituents, R, than 2R. Electron-donating species increase N in both 1R and 2R, while electron-withdrawing groups increase stability.

KW - Band gap

KW - Electronic effect

KW - Singlet-triplet energy gap

KW - Tetrazole-vinylidene germylene

KW - Triplet state

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Novel triplet germylenes in focus: normal vs. abnormal triplet exocyclic tetrazol-5-vinylidene germylenes at DFT

Abstract

Keywords

ASJC Scopus subject areas

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