The photophysical properties of a series of T‐shaped coinage d10 metal complexes, supported by a bis(mesoionic carbene)carbazolide (CNC) pincer ligand, are explored. The series includes a rare new ...example of a tridentate T‐shaped AgI complex. Post‐complexation modification of the AuI complex provides access to a linear cationic AuI complex following ligand alkylation, or the first example of a cationic square planar AuIII−F complex from electrophilic attack on the metal centre. Emissions ranging from blue (CuI) to orange (AgI) are obtained, with variable contributions of thermally‐dependent fluorescence and phosphorescence to the observed photoluminescence. Green emissions are observed for all three gold complexes (neutral T‐shaped AuI, cationic linear AuI and square planar cationic AuIII). The higher quantum yield and longer decay lifetime of the linear gold(I) complex are indicative of increased phosphorescence contribution.
T‐Shaped coinage‐metal complexes: Photoluminescence tuning mediated by a bis(mesoionic carbene)amido pincer ligand for d10 complexes of unusual T‐shape, linear AuI and square planar AuIII.
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New tetranuclear supramolecular precursors (RCCCC)Ag4 (R = i Pr, t Bu, and chx) are employed to construct a series of heterometallic silver(I)–copper(I) alkyl-1,3-diynyl cluster complexes ...(1–9) that bear a common CuAg3 core (normally trigonal-planar, but can be distorted to pyramidal) consolidated by cupro-argentophilic interaction under 3.12 Å, as found in 1 and 2. The photophysical properties of the multinuclear supramolecular precursors and selected complexes have been investigated. The present results strongly suggest that the assembly of medium-nuclearity clusters 3 to 9 is initiated by accretion of additional Ag(I) ions by the ubiquitous CuAg3 template through argentophilic (<3.4 Å) interaction, with cooperative cuprophilic enhancement (<2.76 Å) in the case of compound 9. To our knowledge, the present study provides the first report of conversion of a Group 11 homonuclear cluster into a heteronuclear one of higher nuclearity via inner-core expansion.
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Due to the ubiquity of chirality in nature, chiral self‐assembly involving self‐sorting behaviors has remained as one of the most important research topics of interests. Herein, starting from a ...racemic mixture of SEG‐based (SEG=SEGPHOS) chlorogold(I) precursors, a unique chiral butterfly‐shape hexadecanuclear gold(I) cluster (Au16) with different ratios of RSEG and SSEG ligands is obtained via homoleptic and heterochiral self‐sorting. More interestingly, by employing different chlorogold(I) precursors of opposite chirality (such as RSEG‐Au2 and SBIN‐Au2 (BIN=BINAP)), an unprecedented heteroleptic and heterochiral self‐sorting strategy has been developed to give a series of heteroleptic chiral decanuclear gold(I) clusters (Au10) with propellor‐shape structures. Heterochiral and heteroleptic self‐sorting have also been observed between enantiomers of homoleptic chiral Au10 clusters to result in the heteroleptic chiral Au10 clusters via cluster‐to‐cluster transformation. Incorporation of heteroleptic ligands is found to decrease the symmetry from S4 of homoleptic meso Au10 to C2 of heteroleptic chiral Au10 clusters. The chirality has been transferred from the axial chiral ligands and stored in the heteroleptic gold(I) clusters.
The full potential of the chiral self‐sorting in gold(I)‐sulfido cluster system has been explored for the first time. Different combinations of axial chiral ligands give rise to distinct chiral gold(I)‐sulfido clusters through different types of chiral self‐assembly and self‐sorting processes, evolving from homochiral assembly to heterochiral self‐sorting and the unprecedented heterochiral and heteroleptic self‐sorting.
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4.
A Diverse View of Science to Catalyse Change Urbina-Blanco, César A; Jilani, Safia Z; Speight, Isaiah R ...
Journal of the American Chemical Society,
08/2020, Volume:
142, Issue:
34
Journal Article
Peer reviewed
Open access
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Smart POMs: A surfactant‐encapsulated organic‐grafted polyoxometalate (POM) is synthesized by grafting a photoresponsive azobenzene group to an Anderson‐type POM cluster. Self‐assemblies of the ...hybrid complexes exhibit photocontrolled reversible aggregation and morphological change as a result of photoisomerization‐induced structural alternation (see figure).
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A novel class of chiral luminescent square‐planar platinum complexes with a π‐bonded chiral thioquinonoid ligand is described. Remarkably the presence of this chiral organometallic ligand controls ...the aggregation of this square planar luminophor and imposes a homo‐ or hetero‐chiral arrangement at the supramolecular level, displaying non‐covalent Pt–Pt and π–π interactions. Interestingly these complexes are highly luminescent in the crystalline state and their photophysical properties can be traced to their aggregation in the solid state. A TD‐DFT calculation is obtained to rationalize this unique behavior.
Chiral luminescent square‐planar platinum complexes with a π‐bonded chiral thioquinonoid ligand can control the aggregation of the luminophors and imposes homo‐ or hetero‐chiral arrangements. These complexes are highly luminescent and their photophysical properties can be traced to solid‐state aggregation.
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This paper is concerned with the synthesis and reactions of enantiopure 1,8,9,16-tetraethynyltetraphenylene (3). We obtained 3 in 34% yield through four steps starting from ...1,8,9,16-tetrahydroxytetraphenylene (2a) via a functional group interconversion strategy. On the basis of this chiral “helical” building block, three rigid helical macrocycles 14, 15, and 22 were designed. Complexes 14 and 15 were constructed via coordination-driven self-assembly with platinum(II) complexes 8 and 9b, while 22 cannot be obtained successfully. Then macrocycle 28 was designed on the structural basis of 22 to which octyl chains were introduced, in the hope of improving the solubility of the complex. Macrocycle 28 was finally formed and was characterized by NMR spectroscopy, elemental analysis, and electrospray mass spectrometry. For the enantiopure 15 and 28, circular dichroism (CD) spectra also exhibited chiral properties. Complexes 27 and 28 both exhibited an intense emission band at 621 nm in acetonitrile at 298 K upon excitation at λ > 420 nm.
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There has been mounting concern over the absence of gender equality in the sciences in recent years. This has been accompanied by a broadening of the perspective, in order to address issues of ...equality, diversity and inclusion, relating to a wide range of circumstances in which individuals suffer discrimination. While some progress has been made in some countries, nationally or at the level of institutions, much more needs to be done. The chemical sciences can play a leading role in addressing biases, through 1) becoming a model of good systemic practice in policies, processes, and actions; 2) developing practical skills through training in cultural competence; and 3) promoting a stronger evidence base to uncover both the extent of problems and the degree to which approaches to improve equality, diversity, and inclusion are working.
All inclusive: The chemical sciences can play a leading role in promoting improved equality, diversity and inclusion practices, through 1) becoming a model of good practice; 2) developing practical skills through training in cultural competence; and 3) promoting a stronger evidence base, to uncover both the extent of problems and the degree to which approaches to improvements are working.
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Nucleic acid was found to induce the aggregation of the positively charged pyrene probe (compound 1); as a result, strong pyrene excimer emission was observed. The intensity of the excimer emission ...was dependent on the concentration of the pyrene probe and the oligonucleotide length, sequence, and concentration. These results suggest a new strategy for label-free nucleic acid-based biosensing applications.
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10.
Preface for special issue on Soft Crystals Kato, Masako; Ishii, Kazuyuki; Yam, Vivian W.-W. ...
Journal of photochemistry and photobiology. C, Photochemistry reviews,
June 2022, 2022-06-00, Volume:
51
Journal Article
Peer reviewed
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GEOZS, IJS, IMTLJ, KILJ, KISLJ, NLZOH, NUK, OILJ, PNG, SAZU, SBCE, SBJE, UILJ, UL, UM, UPCLJ, UPUK, ZAGLJ, ZRSKP
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