scholarly journals Exploring the Self-Assembled Tacticity in Aurophilic Polymeric Arrangements of Diphosphanegold(I) Fluorothiolates

Molecules ◽  
2019 ◽  
Vol 24 (23) ◽  
pp. 4422 ◽  
Author(s):  
Moreno-Alcántar ◽  
Salazar ◽  
Romo-Islas ◽  
Flores-Álamo ◽  
Torrens
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Structural Diversity ◽  
Supramolecular Structures ◽  
X Ray Diffraction ◽  
Ligand Effects ◽  
Rational Control ◽  
Solid State Structures ◽  
Further Development ◽  
Aurophilic Interactions

Despite the recurrence of aurophilic interactions in the solid-state structures of gold(I) compounds, its rational control, modulation, and application in the generation of functional supramolecular structures is an area that requires further development. The ligand effects over the aurophilic-based supramolecular structures need to be better understood. This paper presents the supramolecular structural diversity of a series of new 1,3-bis(diphenylphosphane)propane (dppp) gold(I) fluorinated thiolates with the general formula [Au2(SRF)2(μ-dppp)] (SRF = SC6F5 (1); SC6HF4-4 (2); SC6H3(CF3)2-3,5 (3); SC6H4CF3-2 (4); SC6H4CF3-4 (5); SC6H3F2-3,4 (6); SC6H3F2-3,5 (7); SC6H4F-2 (8); SC6H4F-3 (9); SC6H4F-4 (10)). These compounds were synthesized and characterized, and six of their solid-state crystalline structures were determined using single-crystal X-ray diffraction. In the crystalline arrangement, they form aurophilic-bridged polymers. In these systems, the changes in the fluorination patterns of the thiolate ligands tune the aurophilic-induced self-assembly of the compounds causing tacticity and chiral differentiation of the monomers. This is an example of the use of ligand effects on the tune of the supramolecular association of gold complexes.

scholarly journals Investigation of Solvatomorphism and Its Photophysical Implications for Archetypal Trinuclear Au3(1-Methylimidazolate)3

Molecules ◽  
2021 ◽  
Vol 26 (15) ◽  
pp. 4404
Author(s):  
Shengyang Guan ◽  
David C. Mayer ◽  
Christian Jandl ◽  
Sebastian J. Weishäupl ◽  
Angela Casini ◽  
...  
Keyword(s):  
Crystal Structure ◽  
Solid State ◽  
Density Functional ◽  
Bulk Material ◽  
Variable Temperature ◽  
Active Phase ◽  
Solvent Free ◽  
X Ray Diffraction ◽  
X Ray ◽  
Aurophilic Interactions

A new solvatomorph of [Au3(1-Methylimidazolate)3] (Au3(MeIm)3)—the simplest congener of imidazolate-based Au(I) cyclic trinuclear complexes (CTCs)—has been identified and structurally characterized. Single-crystal X-ray diffraction revealed a dichloromethane solvate exhibiting remarkably short intermolecular Au⋯Au distances (3.2190(7) Å). This goes along with a dimer formation in the solid state, which is not observed in a previously reported solvent-free crystal structure. Hirshfeld analysis, in combination with density functional theory (DFT) calculations, indicates that the dimerization is generally driven by attractive aurophilic interactions, which are commonly associated with the luminescence properties of CTCs. Since Au3(MeIm)3 has previously been reported to be emissive in the solid-state, we conducted a thorough photophysical study combined with phase analysis by means of powder X-ray diffraction (PXRD), to correctly attribute the photophysically active phase of the bulk material. Interestingly, all investigated powder samples accessed via different preparation methods can be assigned to the pristine solvent-free crystal structure, showing no aurophilic interactions. Finally, the observed strong thermochromism of the solid-state material was investigated by means of variable-temperature PXRD, ruling out a significant phase transition being responsible for the drastic change of the emission properties (hypsochromic shift from 710 nm to 510 nm) when lowering the temperature down to 77 K.

Gold(I) Complexes Bearing P∩N-Ligands: An Unprecedented Twelve-membered Ring Structure Stabilized by Aurophilic Interactions

2009 ◽  
Vol 64 (11-12) ◽  
pp. 1513-1524 ◽  
Author(s):  
Uwe Monkowius ◽  
Manfred Zabel ◽  
Michel Fleck ◽  
Hartmut Yersin
Keyword(s):  
Solid State ◽  
Ring Structure ◽  
Phosphine Ligands ◽  
X Ray Crystallography ◽  
Aggregation Pattern ◽  
Elemental Analyses ◽  
High Yields ◽  
First Time ◽  
Solid State Structures ◽  
Aurophilic Interactions

The P∩N-ligands Ph2Pqn, 1, Ph2 Piqn, 2, Ph2 Ppym, 3, and the As∩N-ligands Ph2Asqn, 4, Ph2Asiqn, 5, (Ph = phenyl, qn = 8-quinoline, iqn = 1-isoquinoline, pym = 2-pyrimidine) have been synthesized, the ligands 2 and 5 for the first time. Their ligand properties were probed by the synthesis of gold(I) complexes. Reaction with (tht)AuCl (tht = tetrahydrothiophene) yielded the chlorogold complexes Ph2RP-Au-Cl (R = qn, 6; iqn, 7; pym, 8) and Ph2RAs-Au-Cl (R = qn, 9; iqn, 10) in high yields. Further treatment of 7 and 8 with one equivalent of AgBF4 provided the complexes [(Ph2Piqn)Au]BF4, 11, [(Ph2Ppym)Au]BF4, 12, and [(Ph2Piqn)Au(tht)]BF4, 14. For comparison, the previously reported complex [(Ph2Ppy)Au]BF4 (py = pyridine), 13, was re-investigated. The compounds were characterized by elemental analyses, mass spectrometry and NMR spectroscopy. In addition, the solid-state structures of 2, 3, 6, 7, 9 - 14 have been determined by X-ray crystallography. The chloro-gold compounds crystallize in the common rod-like structure known from R3EAuCl (R = aryl, E = P, As) complexes without further aggregation via aurophilic interactions. In all cases the phosphine acts as a monodentate ligand. In the solid state compounds 11 - 13 feature an unprecedented cyclic trinuclear aggregation pattern, in which the Au(I) atoms are linearly coordinated by the bridging phosphine ligands forming a cyclic (P-Au-N)3 arrangement. The resulting twelvemembered ring is further stabilized by Au · · · Au interactions. Due to the presence of these Au · · · Au contacts, 11 - 13 are emissive in the solid state but not in solution

scholarly journals Solid-State Structures and Photoluminescence of Lamellar Architectures of Cu(I) and Ag(I) Paddlewheel Clusters with Hydrogen-Bonded Polar Guests

Molecules ◽  
2021 ◽  
Vol 26 (21) ◽  
pp. 6731
Author(s):  
Haruki Inoue ◽  
Yuga Yamashita ◽  
Yoshiki Ozawa ◽  
Toshikazu Ono ◽  
Masaaki Abe
Keyword(s):  
Solid State ◽  
Diffuse Reflectance Spectroscopy ◽  
X Ray Diffraction ◽  
Uv Illumination ◽  
Near Ir ◽  
Carboxylic Groups ◽  
Dta Analysis ◽  
Non Covalent Interactions ◽  
Solid State Structures ◽  
Covalent Interactions

Two hexanuclear paddlewheel-like clusters appending six carboxylic-acid pendants have been isolated with the inclusion of polar solvent guests: [Cu6(Hmna)6]·7DMF (1·7DMF) and [Ag6(Hmna)6]·8DMSO (2·8DMSO), where H2mna = 2-mercaptonicotininc acid, DMF = N,N’-dimethylformamide, and DMSO = dimethyl sulfoxide. The solvated clusters, together with their fully desolvated forms 1 and 2, have been characterized by FTIR, UV–Vis diffuse reflectance spectroscopy, TG-DTA analysis, and DFT calculations. Crystal structures of two solvated clusters 1·7DMF and 2·8DMSO have been unambiguously determined by single-crystal X-ray diffraction analysis. Six carboxylic groups appended on the clusters trap solvent guests, DMF or DMSO, through H-bonds. As a result, alternately stacked lamellar architectures comprising of a paddlewheel cluster layer and H-bonded solvent layer are formed. Upon UV illumination (λex = 365 nm), the solvated hexasilver(I) cluster 2·8DMSO gives intense greenish-yellow photoluminescence in the solid state (λPL = 545 nm, ΦPL = 0.17 at 298 K), whereas the solvated hexacopper(I) cluster 1·7DMF displays PL in the near-IR region (λPL = 765 nm, ΦPL = 0.38 at 298 K). Upon complete desolvation, a substantial bleach in the PL intensity (ΦPL < 0.01) is observed. The desorption–sorption response was studied by the solid-state PL spectroscopy. Non-covalent interactions in the crystal including intermolecular H-bonds, CH···π interactions, and π···π stack were found to play decisive roles in the creation of the lamellar architectures, small-molecule trap-and-release behavior, and guest-induced luminescence enhancement.

scholarly journals Bis(dicarbollide) Complexes of Transition Metals as a Platform for Molecular Switches. Study of Complexation of 8,8′-Bis(methylsulfanyl) Derivatives of Cobalt and Iron Bis(dicarbollides)

Molecules ◽  
2020 ◽  
Vol 25 (23) ◽  
pp. 5745
Author(s):  
Sergey A. Anufriev ◽  
Sergey V. Timofeev ◽  
Alexei A. Anisimov ◽  
Kyrill Yu. Suponitsky ◽  
Igor B. Sivaev
Keyword(s):  
Solid State ◽  
Transition Metal ◽  
Molecular Switches ◽  
X Ray Diffraction ◽  
Chelate Complexes ◽  
X Ray ◽  
Complexes Of Transition Metals ◽  
Silver Palladium ◽  
Solid State Structures ◽  
Derivatives Of

Complexation of the 8,8′-bis(methylsulfanyl) derivatives of cobalt and iron bis(dicarbollides) [8,8′-(MeS)2-3,3′-M(1,2-C2B9H10)2]− (M = Co, Fe) with copper, silver, palladium and rhodium leads to the formation of the corresponding chelate complexes, which is accompanied by a transition from the transoid to the cisoid conformation of the bis(dicarbollide) complex. This transition is reversible and can be used in design of coordination-driven molecular switches based on transition metal bis(dicarbollide) complexes. The solid-state structures of {(Ph3P)ClPd[8,8′- (MeS)2-3,3′-Co(1,2-C2B9H10)2-κ2-S,S′]} and {(COD)Rh[8,8′-(MeS)2-3,3′-Co(1,2-C2B9H10)2-κ2-S,S′]} were determined by single crystal X-ray diffraction.

Janus-AT Bases:  Synthesis, Self-Assembly, and Solid State Structures

2007 ◽  
Vol 72 (2) ◽  
pp. 466-475 ◽  
Author(s):  
Ali Asadi ◽  
Brian O. Patrick ◽  
David M. Perrin
Keyword(s):  
Solid State ◽  
Self Assembly ◽  
Solid State Structures

Synthesis and solid-state structures of gold(i) complexes of diphosphines

2016 ◽  
Vol 40 (7) ◽  
pp. 6467-6474 ◽  
Author(s):  
Sebastian Molitor ◽  
Christoph Mahler ◽  
Viktoria H. Gessner
Keyword(s):  
Solid State ◽  
Structure Formation ◽  
Gold Complexes ◽  
Solid State Structures ◽  
Aurophilic Interactions

A series of diphosphine bis(gold) complexes were synthesised and the importance of aurophilic interactions for their structure formation was studied.

Copper(II) Complexes of a Tripyridyl Ligand: Anion-Dependent Metallosupramolecular Structures

2013 ◽  
Vol 66 (11) ◽  
pp. 1447 ◽  
Author(s):  
James E. M. Lewis ◽  
James D. Crowley
Keyword(s):  
Mass Spectrometry ◽  
Solid State ◽  
Coordination Polymer ◽  
Elemental Analysis ◽  
Spectroscopic Properties ◽  
Nitrate Salt ◽  
X Ray Diffraction ◽  
X Ray ◽  
Salt Structure ◽  
Solid State Structures

A series of copper(ii) complexes of the ligand 2,6-bis(pyridin-3-ylethynyl)pyridine have been synthesised and characterised by 1H and DOSY NMR, IR and UV-Vis spectroscopies, mass spectrometry, elemental analysis and single crystal X-ray diffraction. In solution these systems display almost identical spectroscopic properties, however the solid state structures are shown to vary widely, depending upon the choice of anion. The tetrafluoroborate salt was revealed to be a discrete Cu2L4 cage-like helicate. The tosylate salt, whilst of the same Cu2L4 stoichiometry, was shown to be a coordination polymer. Finally the nitrate salt structure was observed to be a discrete Cu2L2 metallocycle.

Synthesis, characterization, and application of palladium complexes containing 8-quinolylphosphinite ligands

2010 ◽  
Vol 88 (2) ◽  
pp. 99-103 ◽  
Author(s):  
Earl Cook ◽  
Jason D. Masuda ◽  
Aibing Xia
Keyword(s):  
Solid State ◽  
Single Crystal ◽  
Phenylboronic Acid ◽  
Suzuki Coupling ◽  
Palladium Complexes ◽  
Aryl Halides ◽  
Coupling Reactions ◽  
X Ray Diffraction ◽  
X Ray ◽  
Solid State Structures

Palladium complexes containing 8-quinolylphosphinite ligands have been synthesized and characterized. Their solid state structures were determined by single-crystal X-ray diffraction. They were found to be active catalysts for Suzuki coupling reactions of phenylboronic acid and various aryl halides.

scholarly journals MicroED Elucidation of Diverse Solid-State Packing in a Family of Electron-Deficient Expanded Helicenes

2020 ◽  
Author(s):  
Adrian Samkian ◽  
Gavin R. Kiel ◽  
Christopher G. Jones ◽  
Harrison Bergman ◽  
Julia Oktawiec ◽  
...  
Keyword(s):  
Solid State ◽  
Electron Diffraction ◽  
Rapid Assessment ◽  
Nanometer Scale ◽  
Proof Of Concept ◽  
X Ray Diffraction ◽  
X Ray ◽  
Space Groups ◽  
Indispensable Tool ◽  
Solid State Structures

Solid-state packing plays a defining role in the properties of a molecular organic material, but it is difficult to elucidate in the absence of single crystals that are suitable for X-ray diffraction. Here, we demonstrate the coupling of divergent synthesis with microcrystal electron diffraction (MicroED) for rapid assessment of solid-state packing motifs, using a class of chiral nanocarbons – expanded helicenes – as a proof of concept. Two highly selective oxidative dearomatizations of a readily-accessible helicene provided a divergent route to four electron-deficient analogues containing quinone or quinoxaline units. Crystallization efforts consistently yielded microcrystals that were unsuitable for single crystal X-ray diffraction, but ideal for MicroED. This technique facilitated the elucidation of solid-state structures of all five compounds with <1.1 Å resolution. The otherwise-inaccessible data revealed a range of notable packing behavior, including four different space groups, homochirality in a crystal for a helicene with an extremely low enantiomerization barrier, and nanometer scale cavities. The results of this study suggest that MicroED will soon become an indispensable tool for high-throughput investigations in pursuit of next-generation organic materials.

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