Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking Interactions
Two 1:1 charge-transfer organic complexes were formed using tetrathiafulvalene as a donor and a 9H-fluorenone derivative as acceptor: 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid (complex 1) or 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid methyl ester (complex 2). Both systems crystallize...
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| Format: | Article |
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MDPI AG
2015-06-01
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| Series: | Crystals |
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| Online Access: | http://www.mdpi.com/2073-4352/5/3/283 |
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| author | Amparo Salmerón-Valverde Sylvain Bernès |
| author_facet | Amparo Salmerón-Valverde Sylvain Bernès |
| author_sort | Amparo Salmerón-Valverde |
| collection | DOAJ |
| description | Two 1:1 charge-transfer organic complexes were formed using tetrathiafulvalene as a donor and a 9H-fluorenone derivative as acceptor: 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid (complex 1) or 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid methyl ester (complex 2). Both systems crystallize with alternated donor and acceptor stacks. However, the crystal structure of 1 is influenced by classical hydrogen bonds involving carboxylic acid groups, which force to arrange acceptors as centrosymmetric dimers in the crystal, via R2 2(8) ring motifs, while such a restriction is no longer present in the case of 2, affording thus a different crystal structure. This main difference is reflected in stacking interactions, and, in turn, in the degree of charge transfer observed in the complexes. The degree of charge transfer, estimated using Raman spectroscopy, is δ1 = 0.07 for 1 and δ2 = 0.14 for 2. It thus seems that, at least for the studied complexes, hydrogen bonding is an unfavorable factor for charge transfer. |
| first_indexed | 2024-04-14T00:58:05Z |
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| id | doaj.art-31bf9b7595f54c1295443226a054e3f9 |
| institution | Directory Open Access Journal |
| issn | 2073-4352 |
| language | English |
| last_indexed | 2024-04-14T00:58:05Z |
| publishDate | 2015-06-01 |
| publisher | MDPI AG |
| record_format | Article |
| series | Crystals |
| spelling | doaj.art-31bf9b7595f54c1295443226a054e3f92022-12-22T02:21:30ZengMDPI AGCrystals2073-43522015-06-015328329310.3390/cryst5030283cryst5030283Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking InteractionsAmparo Salmerón-Valverde0Sylvain Bernès1Centro de Química del Instituto de Ciencias, Benemérita Universidad Autónoma de Puebla, Ciudad Universitaria, San Manuel, Puebla, Pue., CP 72570, MexicoInstituto de Física, Benemérita Universidad Autónoma de Puebla, Av. San Claudio y 18 Sur, Puebla, Pue., CP 72570, MexicoTwo 1:1 charge-transfer organic complexes were formed using tetrathiafulvalene as a donor and a 9H-fluorenone derivative as acceptor: 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid (complex 1) or 4,5,7-trinitro-9H-fluoren-9-one-2-carboxylic acid methyl ester (complex 2). Both systems crystallize with alternated donor and acceptor stacks. However, the crystal structure of 1 is influenced by classical hydrogen bonds involving carboxylic acid groups, which force to arrange acceptors as centrosymmetric dimers in the crystal, via R2 2(8) ring motifs, while such a restriction is no longer present in the case of 2, affording thus a different crystal structure. This main difference is reflected in stacking interactions, and, in turn, in the degree of charge transfer observed in the complexes. The degree of charge transfer, estimated using Raman spectroscopy, is δ1 = 0.07 for 1 and δ2 = 0.14 for 2. It thus seems that, at least for the studied complexes, hydrogen bonding is an unfavorable factor for charge transfer.http://www.mdpi.com/2073-4352/5/3/283charge transfertetrathiafulvalenehydrogen bondRaman spectroscopy |
| spellingShingle | Amparo Salmerón-Valverde Sylvain Bernès Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking Interactions Crystals charge transfer tetrathiafulvalene hydrogen bond Raman spectroscopy |
| title | Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking Interactions |
| title_full | Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking Interactions |
| title_fullStr | Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking Interactions |
| title_full_unstemmed | Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking Interactions |
| title_short | Two Closely Related Organic Charge-Transfer Complexes Based on Tetrathiafulvalene and 9H-fluorenone Derivatives. Competition between Hydrogen Bonding and Stacking Interactions |
| title_sort | two closely related organic charge transfer complexes based on tetrathiafulvalene and 9h fluorenone derivatives competition between hydrogen bonding and stacking interactions |
| topic | charge transfer tetrathiafulvalene hydrogen bond Raman spectroscopy |
| url | http://www.mdpi.com/2073-4352/5/3/283 |
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