Au 3 -to-Ag 3 coordinate-covalent bonding and other supramolecular interactions with covalent bonding strength
Abstract
An efficient strategy for designing charge-transfer complexes using coinage metal cyclic trinuclear complexes (CTCs) is described herein. Due to opposite quadrupolar electrostatic contributions from metal ions and ligand substituents, [Au(m-Pz-(i-C3H7)2)]3∙[Ag(m-Tz-(n-C3F7)2)]3 (Pz = pyrazolate, Tz = triazolate) has been obtained and its structure verified by single crystal X-ray diffraction – representing the 1st crystallographically-verified M3@M'3 stacked adduct of monovalent coinage metal CTCs. Abundant supramolecular interactions with aggregate covalent bonding strength arise from a combination of M–M' (Au / Ag), metal–π, π–π interactions and hydrogen bonding in this charge-transfer complex, according to density functional theory analyses, yielding a computed binding energy of 66 kcal mol-1 between the two trimer moieties – a large value for intermolecular interactions between adjacent d10 centres (nearly doubling the value for a recently claimed Au(I) / Cu(I) polar-covalent bond: Proc. Natl. Acad. Sci. U.S.A., 2017, 114, E5042) – which becomes 87 kcal mol-1 with benzene stacking. Surprisingly, DFT analysis suggests that: (a) some other literature precedents should have attained a stacked M3@M'3 product akin to the one herein, with similar or even higher binding energy; and (b) a high overall intertrimer bonding energy by inferior electrostatic assistance, underscoring genuine orbital overlap between M and M' frontier molecularmore »
- Authors:
-
[1];
[1];
[3];
[5];
[1];
[3]
- Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry
- Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry; Norfolk State Univ., Norfolk, VA (United States). Center for Materials Research
- Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry; Yarmouk Univ., Irbid (Jordan). Dept. of Chemistry
- Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry; Univ. of North Texas, Frisco, TX (United States). New College
- Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
- Publication Date:
- Research Org.:
- Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
- OSTI Identifier:
- 1815886
- Grant/Contract Number:
- AC05-00OR22725
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 41; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Lu, Zhou, Chilukuri, Bhaskar, Yang, Chi, Rawashdeh, Abdel-Monem M., Arvapally, Ravi K., Tekarli, Sammer M., Wang, Xiaoping, Cardenas, Christian T., Cundari, Thomas R., and Omary, Mohammad A. Au 3 -to-Ag 3 coordinate-covalent bonding and other supramolecular interactions with covalent bonding strength. United States: N. p., 2020.
Web. doi:10.1039/d0sc02520h.
Lu, Zhou, Chilukuri, Bhaskar, Yang, Chi, Rawashdeh, Abdel-Monem M., Arvapally, Ravi K., Tekarli, Sammer M., Wang, Xiaoping, Cardenas, Christian T., Cundari, Thomas R., & Omary, Mohammad A. Au 3 -to-Ag 3 coordinate-covalent bonding and other supramolecular interactions with covalent bonding strength. United States. https://doi.org/10.1039/d0sc02520h
Lu, Zhou, Chilukuri, Bhaskar, Yang, Chi, Rawashdeh, Abdel-Monem M., Arvapally, Ravi K., Tekarli, Sammer M., Wang, Xiaoping, Cardenas, Christian T., Cundari, Thomas R., and Omary, Mohammad A. Fri .
"Au 3 -to-Ag 3 coordinate-covalent bonding and other supramolecular interactions with covalent bonding strength". United States. https://doi.org/10.1039/d0sc02520h. https://www.osti.gov/servlets/purl/1815886.
@article{osti_1815886,
title = {Au 3 -to-Ag 3 coordinate-covalent bonding and other supramolecular interactions with covalent bonding strength},
author = {Lu, Zhou and Chilukuri, Bhaskar and Yang, Chi and Rawashdeh, Abdel-Monem M. and Arvapally, Ravi K. and Tekarli, Sammer M. and Wang, Xiaoping and Cardenas, Christian T. and Cundari, Thomas R. and Omary, Mohammad A.},
abstractNote = {An efficient strategy for designing charge-transfer complexes using coinage metal cyclic trinuclear complexes (CTCs) is described herein. Due to opposite quadrupolar electrostatic contributions from metal ions and ligand substituents, [Au(m-Pz-(i-C3H7)2)]3∙[Ag(m-Tz-(n-C3F7)2)]3 (Pz = pyrazolate, Tz = triazolate) has been obtained and its structure verified by single crystal X-ray diffraction – representing the 1st crystallographically-verified M3@M'3 stacked adduct of monovalent coinage metal CTCs. Abundant supramolecular interactions with aggregate covalent bonding strength arise from a combination of M–M' (Au / Ag), metal–π, π–π interactions and hydrogen bonding in this charge-transfer complex, according to density functional theory analyses, yielding a computed binding energy of 66 kcal mol-1 between the two trimer moieties – a large value for intermolecular interactions between adjacent d10 centres (nearly doubling the value for a recently claimed Au(I) / Cu(I) polar-covalent bond: Proc. Natl. Acad. Sci. U.S.A., 2017, 114, E5042) – which becomes 87 kcal mol-1 with benzene stacking. Surprisingly, DFT analysis suggests that: (a) some other literature precedents should have attained a stacked M3@M'3 product akin to the one herein, with similar or even higher binding energy; and (b) a high overall intertrimer bonding energy by inferior electrostatic assistance, underscoring genuine orbital overlap between M and M' frontier molecular orbitals in such polar-covalent M–M' bonds in this family of molecules. The Au / Ag bonding is reminiscent of classical Werner-type coordinate-covalent bonds such as H3N: → Ag in [Ag(NH3)2]+, as demonstrated herein quantitatively. Solidstate and molecular modeling illustrate electron flow from the p-basic gold trimer to the p-acidic silver trimer with augmented contributions from ligand-to-ligand’ (LL'CT) and metal-to-ligand (MLCT) charge transfer.},
doi = {10.1039/d0sc02520h},
journal = {Chemical Science},
number = 41,
volume = 11,
place = {United States},
year = {Fri Sep 11 00:00:00 EDT 2020},
month = {Fri Sep 11 00:00:00 EDT 2020}
}
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