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Title: Au 3 -to-Ag 3 coordinate-covalent bonding and other supramolecular interactions with covalent bonding strength

Journal Article · · Chemical Science
DOI:https://doi.org/10.1039/d0sc02520h· OSTI ID:1815886
ORCiD logo [1]; ORCiD logo [1];  [2]; ORCiD logo [3];  [1];  [4]; ORCiD logo [5];  [1]; ORCiD logo [1]; ORCiD logo [3]
  1. Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry
  2. Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry; Norfolk State Univ., Norfolk, VA (United States). Center for Materials Research
  3. Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry; Yarmouk Univ., Irbid (Jordan). Dept. of Chemistry
  4. Univ. of North Texas, Denton, TX (United States). Dept. of Chemistry; Univ. of North Texas, Frisco, TX (United States). New College
  5. Oak Ridge National Lab. (ORNL), Oak Ridge, TN (United States). Neutron Scattering Division
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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.

Research Organization:
Oak Ridge National Laboratory (ORNL), Oak Ridge, TN (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC05-00OR22725
OSTI ID:
1815886
Journal Information:
Chemical Science, Vol. 11, Issue 41; ISSN 2041-6520
Publisher:
Royal Society of ChemistryCopyright Statement
Country of Publication:
United States
Language:
English

References (48)

Mixed-Metal Triangular Trinuclear Complexes:  Dimers of Gold−Silver Mixed-Metal Complexes from Gold(I) Carbeniates and Silver(I) 3,5-Diphenylpyrazolates journal March 2005
Molecular and Electronic Structure of Cyclic Trinuclear Gold(I) Carbeniate Complexes: Insights for Structure/Luminescence/Conductivity Relationships journal June 2014
Unsupported Pt(0)−Tl(I) Bonds in the Simple [Pt(PPh 2 Py) 3 Tl] + Complexes journal January 2001
Blue Phosphors of Dinuclear and Mononuclear Copper(I) and Silver(I) Complexes of 3,5-Bis(trifluoromethyl)pyrazolate and the Related Bis(pyrazolyl)borate journal December 2003
The Cambridge Structural Database
  • Groom, Colin R.; Bruno, Ian J.; Lightfoot, Matthew P.
  • Acta Crystallographica Section B Structural Science, Crystal Engineering and Materials, Vol. 72, Issue 2, p. 171-179 https://doi.org/10.1107/S2052520616003954
journal April 2016
All That Glitters Is Not Gold: A Computational Study of Covalent vs Metallophilic Bonding in Bimetallic Complexes of d 10 Metal Centers—A Tribute to Al Cotton on the Tenth Anniversary of His Passing journal January 2018
On/off luminescence vapochromic selective sensing of benzene and its methylated derivatives by a trinuclear silver( i ) pyrazolate sensor journal January 2011
Influence of Relativistic Effects on Bonding Modes in M(II) Dinuclear Complexes (M = Au, Ag, and Cu) journal November 2017
New Class of Oligonuclear Platinum−Thallium Compounds with a Direct Metal-Metal Bond. 5. Structure Determination of Heterodimetallic Cyano Complexes in Aqueous Solution by EXAFS and Vibrational Spectroscopy journal June 2001
Bonding, Luminescence, Metallophilicity in Linear Au 3 and Au 2 Ag Chains Stabilized by Rigid Diphosphanyl NHC Ligands journal August 2016
Supramolecular Chemistry book January 2009
A briefing on aurophilicity journal January 2008
Perfluoropentacene:  High-Performance p−n Junctions and Complementary Circuits with Pentacene journal July 2004
A thorough benchmark of density functional methods for general main group thermochemistry, kinetics, and noncovalent interactions journal January 2011
Insights into Molecular Structures and Optical Properties of Stacked [Au 3 (RN═CR′) 3 ] n Complexes journal December 2017
Glowing gold rings: solvoluminescence from planar trigold(I) complexes journal April 1998
Solvent-Stimulated Luminescence from the Supramolecular Aggregation of a Trinuclear Gold(I) Complex that Displays Extensive Intermolecular AuċAu Interactions journal June 1997
RETRACTED: DFT challenge of intermetallic interactions: From metallophilicity and metallaromaticity to sextuple bonding journal August 2017
Rational Design of Macrometallocyclic Trinuclear Complexes with Superior π-Acidity and π-Basicity journal February 2008
Electronic and Charge-Transport Properties of the Au 3 (CH 3 N═COCH 3 ) 3 Crystal: A Density Functional Theory Study journal June 2013
Bright Phosphorescence of a Trinuclear Copper(I) Complex:  Luminescence Thermochromism, Solvatochromism, and “Concentration Luminochromism”
  • Dias, H. V. Rasika; Diyabalanage, Himashinie V. K.; Rawashdeh-Omary, Manal A.
  • Journal of the American Chemical Society, Vol. 125, Issue 40 https://doi.org/10.1021/ja036736o
journal September 2003
Periodic and Molecular Modeling Study of Donor−Acceptor Interactions in (dbbpy)Pt(tdt)·TENF and [Pt(dbbpy)(tdt)] 2 ·TENF journal February 2010
Remarkable Aurophilicity and Photoluminescence Thermochromism in a Homoleptic Cyclic Trinuclear Gold(I) Imidazolate Complex journal September 2017
External heavy-atom effect of gold in a supramolecular acid–base π stack journal January 2005
Pt–Mg, Pt–Ca, and Pt–Zn Lantern Complexes and Metal-Only Donor–Acceptor Interactions journal December 2016
Formation of a Fluorous/Organic Biphasic Supramolecular Octopus Assembly for Enhanced Porphyrin Phosphorescence in Air journal March 2015
Revealing Noncovalent Interactions journal May 2010
Gold Is Smaller than Silver. Crystal Structures of [Bis(trimesitylphosphine)gold(I)] and [Bis(trimesitylphosphine)silver(I)] Tetrafluoroborate journal January 1996
Unusual Metal-Metal Bonding in a Dinuclear Pt-Au Complex: Snapshot of a Transmetalation Process journal April 2016
Coinage-Metal-Based Cyclic Trinuclear Complexes with Metal–Metal Interactions: Theories to Experiments and Structures to Functions journal August 2020
Luminescent Chains Formed from Neutral, Triangular Gold Complexes Sandwiching Tl I and Ag I . Structures of {Ag([Au(μ-C 2 ,N 3 -bzim)] 3 ) 2 }BF 4 ·CH 2 Cl 2 , {Tl([Au(μ-C 2 ,N 3 -bzim)] 3 ) 2 }PF 6 ·0.5THF (bzim = 1-Benzylimidazolate), and {Tl([Au(μ-C(OEt)═NC 6 H 4 CH 3 )] 3 ) 2 }PF 6 ·THF, with MAu 6 (M = Ag + , Tl + ) Cluster Cores journal June 2000
Polyhedral Cu 2 O Crystals for Diverse Aryl Alkyne Hydroboration Reactions journal December 2018
Argentophilic Interactions journal November 2014
Bonding in 2D Donor–Acceptor Heterostructures journal May 2019
Intertrimer and Intratrimer Metallophilic and Excimeric Bonding in the Ground and Phosphorescent States of Trinuclear Coinage Metal Pyrazolates:  A Computational Study journal April 2006
Synthesis, Spectroscopic Properties, and Photoconductivity of Black Absorbers Consisting of Pt(Bipyridine)(Dithiolate) Charge Transfer Complexes in the Presence and Absence of Nitrofluorenone Acceptors journal November 2014
Kinetically Controlled Self-Assembly of Phosphorescent Au III Aggregates and Ligand-to-Metal–Metal Charge Transfer Excited State: A Combined Spectroscopic and DFT/TDDFT Study journal July 2019
Do Special Noncovalent π–π Stacking Interactions Really Exist? journal April 2008
Alteration of the Aurophilic Interactions in Trimeric Gold(I) Compounds through Charge Transfer. Behavior of Solvoluminescent Au 3 (MeNCOMe) 3 in the Presence of Electron Acceptors journal April 2001
Heterotetrametallic Re–Zn–Zn–Re Complex Generated by an Anionic Rhenium(I) β-Diketiminate journal December 2018
Tuning the Luminescent Properties of a Ag/Au Tetranuclear Complex Featuring Metallophilic Interactions via Solvent-Dependent Structural Isomerization journal October 2016
Cooperativity in Noncovalent Interactions journal February 2016
Gold(I) and Silver(I) Mixed-Metal Trinuclear Complexes:  Dimeric Products from the Reaction of Gold(I) Carbeniates or Benzylimidazolates with Silver(I) 3,5-Diphenylpyrazolate journal August 2006
Raising the Bar in Aromatic Donor–Acceptor Interactions with Cyclic Trinuclear Gold(I) Complexes as Strong π-Donors journal November 2018
Combining Aurophilic Interactions and Halogen Bonding To Control the Luminescence from Bimetallic Gold−Silver Clusters journal December 2009
Supermolecules by Design journal November 1999
Metal Effect on the Supramolecular Structure, Photophysics, and Acid−Base Character of Trinuclear Pyrazolato Coinage Metal Complexes † journal November 2005
Solventless Supramolecular Chemistry via Vapor Diffusion of Volatile Small Molecules upon a New Trinuclear Silver(I)-Nitrated Pyrazolate Macrometallocyclic Solid: An Experimental/Theoretical Investigation of the Dipole/Quadrupole Chemisorption Phenomena journal November 2013

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