An in-depth study of mechanochromic and thermochromic luminescent copper iodide clusters exhibiting structural polymorphism is reported gives new insights into the origin luminescence properties. The two different crystalline polymorphs exhibit distinct properties with one being green emissive other yellow emissive. Upon mechanical grinding, only exhibits great modification its emission from to yellow. Interestingly, photophysical resulting partially amorphous crushed compound are closed...

Three copper(I) iodide clusters coordinated by different phosphine ligands formulated [Cu(4)I(4)(PPh(3))(4)] (1), [Cu(4)I(4)(Pcpent(3))(4)] (2), and [Cu(4)I(4)(PPh(2)Pr)(4)] (3) (PPh(3) = triphenylphosphine, Pcpent(3) tricyclopentylphosphine, PPh(2)Pr diphenylpropylphosphine) have been synthesized characterized (1)H (31)P NMR, elemental analysis single crystal X-ray diffraction analysis. They crystallize in space groups, namely, monoclinic P21/c, cubic Pa ̅3, tetragonal I ̅42m for 1, 2, 3,...

A novel discrete [Ag21{S2P(OiPr)2}12](PF6) nanocluster has been synthesized and characterized by single-crystal X-ray diffraction also NMR spectroscopy ((1)H, (31)P), ESI mass spectrometry, other analytic techniques (XPS, EDS, UV/Vis spectroscopy). The Ag21 skeleton an unprecedented silver-centered icosahedron that is capped eight additional metal atoms. whole framework protected twelve dithiophosphate ligands. According to the spherical Jellium model, stability of monocationic can be...

An unprecedented air-stable, nanospheric polyhydrido copper cluster, [Cu20H11(S2P(O(i)Pr)2)9] (1H), which is the first example of an elongated triangular orthobicupola array Cu atoms having C3h symmetry, was synthesized and characterized. Its composition primarily determined by electrospray ionization mass spectrometry, it fully characterized (1)H, (2)H, (31)P NMR spectroscopy single-crystal X-ray diffraction (XRD). The structure complex 1H can be expressed in terms a trigonal-bipyramidal...

An original copper(I) iodide cluster of novel geometry obtained by using a diphosphine ligand is reported and formulated [Cu6I6(PPh2(CH2)3PPh2)3] (1). Interestingly, this sort "eared cubane" based on the [Cu6I6] inorganic core can be viewed as combination two known [Cu4I4] units, namely, cubane open-chair isomeric geometries. The synthesis, structural photophysical characterisations, well theoretical study copper along with derived (3) (2) [Cu4I4(PPh3)4] forms, were investigated. A new...

The syntheses of the first rhombicuboctahedral copper polyhydride complexes [Cu28 (H)15 (S2 CNR)12 ]PF6 (NR=N(n) Pr2 or aza-15-crown-5) are reported. These were analyzed by single-crystal X-ray and one neutron diffraction. core each hydride nanoparticle comprises central interstitial eight outer-triangular-face-capping hydrides. A further six face-truncating hydrides form an unprecedented bridge between inner outer atom arrays. irregular Cu4 tetrahedron is encapsulated within Cu24 cage,...

An air- and moisture-stable nanoscale polyhydrido copper cluster [Cu32 (H)20 {S2 P(OiPr)2 }12 ] (1H ) was synthesized structurally characterized. The molecular structure of 1H exhibits a hexacapped pseudo-rhombohedral core 14 Cu atoms sandwiched between two nestlike triangular cupola fragments (2×9) in an elongated gyrobicupola polyhedron. discrete Cu32 is stabilized by 12 dithiophosphate ligands record number 20 hydride ligands, which were found high-resolution neutron diffraction to...

Abstract The first atomically and structurally precise silver‐nanoclusters stabilized by Se‐donor ligands, [Ag 20 {Se 2 P(O i Pr) } 12 ] ( 3 ) 21 P(OEt) + 4 ), were isolated ligand replacement reaction of {S 1 respectively. Furthermore, doping reactions with Au(PPh )Cl resulted in the formation [AuAg 5 ). Structures , determined single‐crystal X‐ray diffraction. anatomy cluster an Ag core having C symmetry is very similar to that its dithiophosphate analogue . Clusters exhibit Au@Ag O h...

The first structurally characterized copper cluster with a Cu13 centered cuboctahedral arrangement, model of the bulk fcc structure, was observed in [Cu13 (S2 CNn Bu2 )6 (C≡CR)4 ](PF6 ) (R=C(O)OMe, C6 H4 F) nanoclusters. Four eight triangular faces cuboctahedron are capped by acetylide groups μ3 fashion, and each six square is bridged dithiolate ligand μ2 ,μ2 which leads to truncated tetrahedron twelve sulfur atoms. DFT calculations fully consistent description these clusters as two-electron...

Abstract A polyhydrido copper nanocluster, [Cu 20 H 11 {Se 2 P(O i Pr) } 9 ] ( ), which exhibits an intrinsically chiral inorganic core of C 3 symmetry, was synthesized from achiral {S 1 ) h symmetry by a ligand‐exchange method. The structure has distorted cuboctahedral Cu 13 core, two triangular faces are capped along the axis, one 6 cupola and other single atom. framework is further stabilized diselenophosphate hydride ligands. number hydride, phosphorus, selenium resonances their...

The synthesis and structural determination of a silver nanocluster [Ag20 {S2 P(OiPr)2 }12 ] (2), which contains an intrinsic chiral metallic core, is produced by reduction one ion from the eight-electron superatom complex [Ag21 ](PF6 ) (1) borohydrides. Single-crystal X-ray analysis displays Ag20 core pseudo C3 symmetry comprising silver-centered Ag13 icosahedron capped seven atoms. Its n-propyl derivative, P(OnPr)2 (3), can also be prepared treatment silver(I) salts dithiophosphates in...

Luminescent materials based on copper complexes are currently receiving increasing attention because of their rich photophysical properties, opening a wide field applications. The iodide clusters formulated [Cu4I4L4] (L = ligand), particularly relevant for the development multifunctional luminescence stimuli-responsive properties. In this context, controlling and modulating properties is crucial can only be achieved by thorough understanding origin optical We thus report here, comparative...

Three bimetallic platinum/silver nanoclusters, PtAg20(dtp)12 (1), Pt2Ag33(dtp)17 (2), and Pt3Ag44(dtp)22 (3) (dtp: dipropyl dithiophosphate), with cluster electron counts of 8, 16, 22, respectively, were produced via a one-phase coreduction method. Single-crystal X-ray structures reveal that their inner cores can be visualized as consisting one, two, three centered icosahedral Pt@Ag12 units, respectively. In 2 3, these units are vertex-sharing assembled linearly. Intriguingly, the...

Recent reports on hydride-doped noble metal nanoclusters strongly suggest that the encapsulated hydride is a part of superatom core, but no accurate location could be experimentally proved, so far. We report herein eight-electron platinum/silver alloy nanocluster in which position four-coordinated was determined by neutron diffraction for first time. X-ray structures [PtHAg19(dtp/desp)12] (dtp = S2P(OnPr)2, 1; dsep Se2P(OiPr)2, 2) describe central platinum (PtH) unit within distorted Ag12...

The first hydride-containing 2-electron palladium/copper alloys, [PdHCu11 {S2 P(Oi Pr)2 }6 (C≡CPh)4 ] (PdHCu11 ) and [PdHCu12 }5 PO(Oi Pr)} (PdHCu12 ), are synthesized from the reaction of [PdH2 Cu14 (C≡CPh)6 (PdH2 with trifluoroacetic acid (TFA). X-ray diffraction reveals that PdHCu11 PdHCu12 kernels consist a central PdH unit encapsulated within vertex-missing Cu11 cuboctahedron complete Cu12 cuboctahedron, respectively. DFT calculations indicate both can be considered as axially-distorted...

Up to three hydrides can be incorporated as interstitial dopants in centered icosahedral cores. These move easily within their cage.

Abstract The exploration of ligated metal clusters’ chemical space is challenging, partly owing to an insufficiently targeted access reactive clusters. Now, dynamic mixtures clusters, defined as living libraries, are obtained through organometallic precursor chemistry. libraries populated with interrelated including transient and highly ones, well more accessible but less species. Their evolutions upon perturbation substrate molecules monitored information gained without separation the Here...

The reaction of (CpReH(2))(2)B(4)H(4) with monoborane leads to the sequential formation (CpRe)(2)B(n)()H(n)() (n = 7-10, 1-4). These species adopt closed deltahedra same total connectivities as closo-borane anions [B(n)()H(n)()](2)(-), n 9-12, but flattened geometries rather than spherical shapes. rhenaborane clusters are characterized by high metal coordination numbers, Re-Re cross-cluster distances within single bond range, and formal cluster electron counts three skeletal pairs short that...

Reactions of Cu(I) salts with Na(S2CR) (R = NnPr2, NEt2, aza-15-crown-5), and (Bu4N)(BH4) in an 8:6:1 ratio CH3CN solution at room temperature yield the monocationic hydride-centered octanuclear CuI clusters, [Cu8(H){S2CR}6](PF6) 1H; 2H; aza-15-crown-5, 3H). Further reactions 1 equiv produced neutral heptanuclear copper [Cu7(H){S2CR}6] 4H; 5H; 6H) clusters 4–6 can also be generated from reaction Cu(BF4)2, Na(S2CR), a 7:6:8 molar CH3CN. Reformation cationic CuI8 by adding salt to Cu7 is...

We report the synthesis, characterization, crystal structures, nonlinear-optical (NLO) properties, and density functional theory (DFT) calculations of nickel(ii) copper(ii) complex based ONO tridentate Schiff base ligands: two mononuclear compounds, [Ni(An-ONO)(NC5H5)] (5) [Cu(An-ONO)(4-NC5H4C(CH3)3)] (6), heterobimetallic species, [M(Fc-ONO)(NC5H5)] (M = Ni, 7; Cu, 8), where An-ONOH2 (3) Fc-ONOH2 (4) are 1 : condensation products 2-aminophenol p-anisoylacetone ferrocenoylacetone,...

The structure of a nanospheric polyhydrido copper cluster, [Cu20(H)11{S2P(OiPr)2}9], was determined by single-crystal neutron diffraction. Cu20 cluster consists an elongated triangular orthobicupola constructed from 18 Cu atoms that encapsulate [Cu2H5]3– ion with exceptionally short Cu–Cu distance. 11 hydrides in the display three different coordination modes to atoms: six μ3-hydrides pyramidal geometry, two μ4-hydrides tetrahedral cavity, and unprecedented near square-planar geometry. data...

Three hitherto unknown eight-electron rhodium/silver alloy nanoclusters, [RhAg21{S2P(OnPr)2}12] (1), [RhHAg20{S2P(OnPr)2}12] (2), and [RhH2Ag19{S2P(OnPr)2}12] (3), have been isolated fully characterized. Cluster 1 contains a regular Rh@Ag12 icosahedral core, whereas 2 3 exhibit distorted RhH@Ag12 RhH2@Ag12 cores. The single-crystal neutron structure of located the encapsulated hydride at center an enlarged RhAg3 tetrahedron. A similar position was found by diffraction for one hydrides in 3,...

The first hydride-doped Pd/Ag superatoms stabilized by selenolates are reported: [PdHAg19(dsep)12] [dsep = Se2P(OiPr)2] 1 and [PdHAg20(dsep)12]+ 2. was derived from the targeted transformation of [PdHAg19(dtp)12] [dtp S2P(OiPr)2] ligand exchange, whereas 2 obtained addition trifluoroacetic acid to 1, resulting in a symmetric redistribution capping silver atoms. transformations all achieved while retaining an 8-electron superatomic configuration. VT-NMR attests good stability NCs solution,...

Reactions of Ag(I) salt, NH4(E2P(OR)2) (R = iPr, Et; E Se, S), and NaBH4 in a 7:6:1 ratio CH2Cl2 at room temperature, led to the formation hydride-centered heptanuclear silver clusters, [Ag7(H){E2P(OR)2}6] Se (3): R S(4). The reaction [Ag10(E){E2P(OR)2}8] with produced [Ag8(H){E2P(OR)2}6](PF6) (1): S(2)), which can be converted clusters 3 4, respectively, via addition 1 equiv borohydride. Intriguingly 2 regenerated adding Ag(CH3CN)4PF6 solution compounds respectively. All complexes have been...