Total Structure, Electronic Structure and Catalytic Hydrogenation Activity of Metal-Deficient Chiral Polyhydride Cu57 Nanoclusters.

Accurate identifying and in-depth understanding of the defect sites in a working nanomaterial could hinge on establishing specific defect-activity relationships. Yet, atomically precise coinage-metal nanoclusters (NCs) possessing surface vacancy defects are scarce primarily owing to challenges in the synthesis and isolation of such defective NCs. Herein we report a mixed-ligand strategy to synthesizing an intrinsically chiral and metal-deficient copper hydride-rich NC [Cu57 H20 (PET)36 (TPP)4 ]+ (Cu57 H20 ). Its total structure (including hydrides) and electronic structure are well established by combined experimental and computational results. Crystal structure reveals Cu57 H20 features a cube-like Cu8 kernel embedded in a corner-missing metal-ligand shell of Cu49 (PET)36 (TPP)4 . Single Cu vacancy defect site occurs at one corner of the shell, evocative of mono-lacunary polyoxometalates. Theoretical calculations demonstrate that the above-mentioned point vacancy causes one surface hydride exposed as an interfacial capping µ3 -H- , which is accessible in chemical reaction, as proved by deuterated experiment. Moreover, Cu57 H20 shows catalytic activity in the hydrogenation of nitroarene. The success of this work opens the way for the research on well-defined chiral metal-deficient Cu and other metal NCs, including exploring their application in asymmetrical catalysis.

Secondary hierarchical complexity in double-stranded cluster helicates covered by NNNNN type pincer ligands.

We designed and synthesized a new tripyridine dipyrrolide pincer ligand, which could be doubly deprotonated to provide five-nitrogen-donor sites and then utilized to prepare a subnanometric chiral silver cluster. The cluster belongs to an S4 point group and shows a double-stranded helicate. DFT calculations were performed to analyze the electronic structure of the cluster. Interestingly, through hierarchical intercluster interactions, the cluster helicates evolve into complex secondary structures including a right-handed helix and a folded sheet, both of which are reminiscent of secondary structures of proteins, i.e., an α-helix and an antiparallel ß-sheet.

Multi-layer 3D Chirality and Double-Helical Assembly in a Copper Nanocluster with a Triple-Helical Cu15 Core.

Conceptually mimicking biomolecules' ability to construct multiple-helical aggregates with emergent properties and functions remains a long-standing challenge. Here we report an atom-precise 18-copper nanocluster (NC), Cu18 H(PET)14 (TPP)6 (NCS)3 (Cu18 H) which contains a pseudo D3 -symmetrical triple-helical Cu15 core. Structurally, Cu18 H may be also viewed as sandwich type of sulfur-bridged chiral copper cluster units [Cu6 -Cu6 -Cu6 ], endowing three-layered 3D chirality. More importantly, the chiral NCs are aggregated into an infinite double-stranded helix supported by intra-strand homonuclear C-H⋅⋅⋅H-C dihydrogen contacts and inter-strand C-H/π and C-H/S interactions. The unique multi-layered 3D chirality and the double-helical assembly of Cu18 H are evocative of DNA. Moreover, the collective behaviours of the aggregated NCs not only exhibit crystallization-induced emission enhancement (CIEE) and aggregation-induced emission enhancement (AIEE) effects in the deep-red region, but also efficiently catalyze electron transfer (ET) reaction. This study thus presents that hierarchical assemblies of atomically defined copper NCs could be intricate as observed for important biomolecules like DNA with emergent properties arising from aggregated behaviours.

Controllable spontaneous resolution in ultrasmall Cu-Ag bimetallic cluster ion pairs from achiral components.

Bimetallic cluster ion pairs containing a quaternary phosphonium and an ultrasmall Cu2Ag3 anionic cluster protected by thiolates: (PPh3R'')[Cu2Ag3(SR')6] (R'SH = cyclohexylthiol (CySH), R'' = Ph, 1; Me, 2; Et, 3; Pr, 4; R'SH = tert-butylthiol (tBuSH) and R'' = Ph, 5) were reported. Without any chiral source, 1 crystallizes as conglomerate crystals with homochiral packings and spontaneous resolution occurs, while four other clusters 2-5 crystallize as racemic crystals with heterochiral packings. These results indicate that racemic and homochiral crystallization in the cluster system could be controlled through fine-tuning internal achiral structural components.

Unusual Intramolecular Motion of ReH92- in K2ReH9 Crystal: Circle Dance and Three-Arm Turnstile Mechanisms Revealed by Computational Studies.

The nonahydridorhenate dianion ReH92- is a unique rhenium polyhydride complex due to its remarkably high coordination number; however, its detailed polytopal rearrangement process in either solution or crystal is so far unclear. In this work, our quantum chemical calculations have identified two previously unreported fluxional mechanisms for the ReH92- dianion in the K2ReH9 crystal: three-arm turnstile rotation and circle dance mechanism. These two polytopal rearrangements in the crystal offer an alternative interpretation to the pulse and wide-line NMR spectra (Farrar et al. J. Chem. Phys. 1969, 51, 3595). The previously postulated hindered rotation of the whole ReH92- dianion in K2ReH9 (White et al. J. Chem. Soc., Faraday Trans. 2 1972, 68, 1414) turns out to be a combination of the above-mentioned two elementary fluxional processes. In addition, our calculations have confirmed the Muetterties' D3h⇌C4v rearrangement as the intramolecular motion for the ReH92- dianion in solution.

Observation of a bcc-like framework in polyhydrido copper nanoclusters.

Cu is well-known to adopt a face-centered cubic (fcc) structure in the bulk phase. Ligand-stabilized Cu nanoclusters (NCs) with atomically precise structures are an emerging class of nanomaterials. However, it remains a great challenge to have non-fcc structured Cu NCs. In this contribution, we report the syntheses and total structure determination of six 28-nuclearity polyhydrido Cu NCs: [Cu28H16(dppp)4(RS)4(CF3CO2)8] (dppp = 1,3-bis(diphenylphosphino)propane, RSH = cyclohexylthiol, 1; tert-butylthiol, 3; and 2-thiophenethiol, 4) and [Cu28H16(dppe)4(RS)4(CH3CO2)6Cl2] (dppe = 1,2-bis(diphenylphosphino)ethane, RSH = (4-isopropyl)thiophenol, 2; 4-tert-butylbenzenethiol, 5; and 4-tert-butylbenzylmercaptan, 6). Their well-defined structures solved by X-ray single crystal diffraction reveal that these 28-Cu NCs are isostructural, and the overall metal framework is arranged as a sandwich structure with a core-shell Cu2@Cu16 unit held by two Cu5 fragments. One significant finding is that the organization of 18 Cu atoms in the Cu2@Cu16 could be regarded as an incomplete and distorted version of 3 × 2 × 2 "cutout" of the body-centered cubic (bcc) bulk phase, which was strikingly different to the fcc structure of bulk Cu. The bcc framework came as a surprise, as no bcc structures have been previously observed in Cu NCs. A comparison with the ideal bcc arrangement of 18 Cu atoms in the bcc lattice suggests that the distortion of the bcc structure results from the insertion of interstitial hydrides. The existence, number, and location of hydrides in these polyhydrido Cu NCs are established by combined experimental and DFT results. These results have significant implications for the development of high-nuclearity Cu hydride NCs with a non-fcc architecture.

Describing Polytopal Rearrangement Processes of Octacoordinate Structures. I. Renewed Insights into Fluxionality of the Rhenium Polyhydride Complex ReH5(PPh3)2(Pyridine).

Hydride ligands of transition metal polyhydride complexes with a high coordination number are prone to fluxionality leading to interesting structural dynamics. However, the underlying polytopal rearrangement pathways have been rarely studied. Based on quantum chemical calculations carried out in this work with density functional theory and coupled-cluster theory, two new fluxional mechanisms have been identified for the rhenium polyhydride complex ReH5(PPh3)2(pyridine) to jointly account for two consecutive coalescence events in the variable-temperature NMR spectra upon heating: lateral and basal three-arm turnstile rotation. The frequently cited pseudorotation in ReH5(PPh3)2(pyridine) (Lee et al. Inorg. Chem. 1996, 35, 695) turns out to be a three-step process including two lateral three-arm turnstile steps and one basal turnstile step in between. The new fluxional mechanisms discovered in this work may also exist in other transition metal polyhydrides.

New protective ligands for atomically precise silver nanoclusters.

Atomically precise silver nanoclusters (NCs) have emerged as a hot topic attracting immense research interest. Protecting ligands are needed for direct capping on cluster surfaces in order to prevent aggregation and to stabilize NCs. It has been demonstrated that protective ligands are critical to determining the sizes, structures and properties of silver NCs. The past decades have witnessed conventionally used organic ligands (thiolates/selenols, phosphines and alkynyls) and inorganic ligands (chalcogens and halogens) being extensively used to passivate NC surfaces. However, only in the most recent years have new-type protecting ligands beyond the conventional ones begun to be introduced in the protecting sphere of new functional silver NCs. The present Frontier article covers the most recent examples of some new protective agents for well-defined silver NCs. We describe four classes of novel silver NCs stabilized by newly-developed surface ligands, namely, nitrogen-donor organic ligands, oxygen-donor inorganic ligands, metalloligands and macrocyclic hosts, paying attention to the synthesis, structures and properties of these silver NCs. This Frontier article will hopefully attract more cluster scientists to explore more freshly ligated atomically precise silver NCs with novel structures and properties in the years ahead. The literature survey in this review is based on publications up to February 2020. Some suggestions for future directions in this field are also given.

Recent Progress in Inorganic Anions Templated Silver Nanoclusters: Synthesis, Structures and Properties.

Over recent years, research on the ligand-protected silver clusters have gained significant interest owing to their unique potential applications in catalysis, organic optoelectronics, and luminescent materials. However, the synthesis of structurally precise high-nuclearity silver nanoclusters is still challenging and become one of the prime interests of chemists. The controllable synthesis of high-nuclearity silver nanoclusters involves the ingenious use of capping ligands or/and templating agents. Thereinto, the main role of the templating agents is to promote the order arrangement of silver ions around them to form discrete molecules. Our lab has performed comprehensive studies on the ligand-protected silver clusters in the past eight years. This review highlights recent progress in the use of inorganic template anions, silver precursors, solvents, and the ligand types in synthesizing high-nuclearity silver nanoclusters. Furthermore, some interesting photo- and electrochemical properties revealed by silver clusters including luminescent thermochromism, electrical conductivity, and electrochemical reduction of H2 O2 have been also summarized.

Enhanced CO2 capture by reducing cation-anion interactions in hydroxyl-pyridine anion-based ionic liquids.

In this work, an efficient strategy for improving CO2 capture based on anion-functionalized ionic liquids (ILs) by reducing cation-anion interactions in ILs was reported. The influence of the cationic species on CO2 absorption was investigated using 2-hydroxyl pyridium anions ([2-Op]) as a probe. CO2 capture experiments indicated that the CO2 absorption capacity in [2-Op] anion-based ILs varied from 0.94 to 1.69 mol CO2 per mol IL at 30 °C and 1 atm. Spectroscopic analysis and quantum chemical calculations suggested that the increase of the CO2 absorption capacity may be ascribed to the reduction of the strength of cation-anion interactions in ILs, and stronger cation-anion interactions would make one CO2 site in the [2-Op] anion inactive. Furthermore, the effect of the cation unit on the anion was evidenced by FT-IR spectra, implying that strong interactions between ions may lead to the decrease of the IR absorption wavenumber of hydroxy pyridium and work against CO2 capture. Following this strategy, it was finally found that [Ph-C8eim][2-Op] (Ph-C8eim = 1-N-ethyl-3-N-octyl-2-phenylimidazolium) with weaker cation-anion interactions exhibited a significant increase in the CO2 uptake capacity, and extremely high capacities of 1.69 and 1.83 mol CO2 per mol IL could be achieved at 30 and 20 °C, respectively. The study presented here would be helpful for further designing novel and effective ILs for advancing CO2 capturing performance.

Tethered sensitizer-catalyst noble-metal-free molecular devices for solar-driven hydrogen generation.

Inspired by natural photosynthesis in an organized assembly, compact H2-evolving molecular devices, which tether sensitizer and catalyst modules in one single molecule, present an opportunity to overcome the diffusion limit required for multi-component molecular systems, and increase intramolecular electron transfer rates from the photoactivated unit to the catalytic center to improve H2-evolving efficiency. Thereinto absolutely noble-metal free H2-evolving molecular devices are of particular interest because they don't contain precious and scarce noble-metal based components. This Frontier article focuses specifically on the recent advances in the design, synthesis, and photocatalytic properties of all-abundant-element molecular devices for photoinduced H2 generation via intramolecular processes. Some challenges and suggestions for future directions in this field are also illustrated.

The Difference Se Makes: A Bio-Inspired Dppf-Supported Nickel Selenolate Complex Boosts Dihydrogen Evolution with High Oxygen Tolerance.

Inspired by the metal active sites of [NiFeSe]-hydrogenases, a dppf-supported nickel(II) selenolate complex (dppf=1,1'-bis(diphenylphosphino)ferrocene) shows high catalytic activity for electrochemical proton reduction with a remarkable enzyme-like H2 evolution turnover frequency (TOF) of 7838 s-1 under an Ar atmosphere, which markedly surpasses the activity of a dppf-supported nickel(II) thiolate analogue with a low TOF of 600 s-1 . A combined study of electrochemical experiments and DFT calculations shed light on the catalytic process, suggesting that selenium atom as a bio-inspired proton relay plays a key role in proton exchange and enhancing catalytic activity of H2 production. For the first time, this type of Ni selenolate-containing electrocatalyst displays a high degree of O2 and H2 tolerance. Our results should encourage the development of the design of highly efficient oxygen-tolerant Ni selenolate molecular catalysts.

Small size yet big action: a simple sulfate anion templated a discrete 78-nuclearity silver sulfur nanocluster with a multishell structure.

A discrete 78-nucleus silver-sulfur nanocluster with a sulfate-centered multishell structure was isolated and characterized. Its crystal structure revealed 18 and 60 Ag atoms in the inner and outer shell, respectively. The inner shell of 18-nuclearity Ag atoms is a very rare convex polyhedron featuring an elongated triangular orthobicupola. The incorporation of a sulfate anion and multishell arrangement in the nanocluster led to a dramatic decrease in the band gap (Eg = 1.40 eV). Our study showed that simple anions can also induce the formation of high-nuclearity silver clusters with excellent optical properties.

Silver-Sulfur Hybrid Supertetrahedral Clusters: The Hitherto Missing Members in the Metal-Chalcogenide Tetrahedral Clusters.

The synthesis of Group 11 metal chalcogenide supertetrahedral clusters (SCs) still remains a great challenge mainly due to the high tendency of metal aggregation through metallophilicity and global charge balance. Demonstrated herein are the preparation, crystallographic characterization, and optical properties of two stable silver-sulfur SCs through ligand-control; one as a discrete zero-dimensional (0D) V3,4-type cluster and the other as a one-dimensional (1D) zigzag chain extended by alternating V3,2-type clusters. The notation Vn,m (where n is the number of metal layers, and m is the number of vacant corners) is used to describe a new series of vacant-corner SCs, which can be derived from the regular Tn clusters. The existence of vacant-corner-type SCs may be ascribed to the low valence and tri-coordinated environment of silver ions. These are the first representatives of structurally determined silver-sulfur tetrahedral clusters thus far. This work enriches the coinage-metal chalcogenide tetrahedral cluster portfolio, discovers vacant-corner SCs present in silver-sulfur hybrid tetrahedral clusters, and provides effective means for further development of Group 11 coinage-metal chalcogenide SCs.

A square-planar nickel dithiolate complex as an efficient molecular catalyst for the electro- and photoreduction of protons.

A square-planar nickel(ii) dithiolate complex is an active molecular catalyst for both photoreduction of protons from water with a turnover number (>1500) and electroreduction of protons from weakly acidic solutions with remarkable turnover frequencies (5575 s-1 at -1.92 V and 1441 s-1 at -1.61 V vs. SCE). DFT calculations provide in-depth insight into the catalytic cycle of the electrochemical reaction, suggesting that the sulfur atoms play crucial roles in proton exchange and hydrogen formation.

Photocatalytic water reduction from a noble-metal-free molecular dyad based on a thienyl-expanded BODIPY photosensitizer.

A noble-metal-free molecular dyad was constructed by anchoring a thienyl-expanded BODIPY photosensitizer (PS) to a cobaloxime catalyst, which gives a 2.5-fold increase in the TON, and a 3-fold enhancement in the quantum efficiency as compared to the multicomponent catalytic system for the generation of hydrogen via the reduction of water. The stability of PS was expected to improve by introducing the thienyl moiety into the BODIPY core.

The relationship between the boron dipyrromethene (BODIPY) structure and the effectiveness of homogeneous and heterogeneous solar hydrogen-generating systems as well as DSSCs.

A series of boron dipyrromethene (BODIPY) dyes (B1­B5) having H atoms at 2,6-positions or heavy-atom I at 2-/2,6-positions, and an ortho- or a para-COOH substituted phenyl moiety at the 8-position on the BODIPY core were synthesized and characterized. These organic dyes were applied for investigating the relationship between the BODIPY structure and the effectiveness of homogeneous and heterogeneous visible-light-driven hydrogen production as well as dye-sensitized solar cells (DSSCs). For the homogeneous photocatalytic hydrogen production systems with a cobaloxime catalyst, the efficiency of hydrogen production could be tuned by substituting with heavy atoms and varying carboxyl group orientations of BODIPYs. As a result, B5 containing two I atoms and an ortho-COOH anchoring group was the most active one (TONs = 197). The activity of hydrogen generation followed the order B5 > B3 > B2 > B1 = B4 = 0. An interesting "ortho-position effect" was observed in the present homogeneous systems, i.e., substitution groups were located at the ortho-position and higher hydrogen production activities were obtained. For the heterogeneous hydrogen production systems with a platinized TiO2 catalyst, the effectiveness of hydrogen evolution was highly influenced by the intersystem crossing efficiency, molar absorptivity and positions of the anchoring group of dyes. Thus, B3 having two core iodine atoms and a para-COOH group with TONs of 70 excelled other BODIPYs and the TONs of hydrogen generation showed the trend of B3 > B5 > B2 > B1 = B4 = 0. The results demonstrate that the present photocatalytic H2 production proceeds with higher efficiency and stability in the homogeneity than in the heterogeneity. In the case of DSSCs, the overall cell performance of BODIPY chromophores was highly dependent on both the absence or the presence of iodine atoms on the BODIPY core and ­COOH anchoring positions. The B1­TiO2 system showed the best cell performance, because the most effective surface binding mode is allowed with this structure. This is also in contrast with the case of dye-sensitized solar H2 generation, in which B3 was the most efficient chromophore. The differences between dye-sensitized hydrogen-generating systems and DSSCs may be due to rates of electron transfer and the dye aggregation tendency.

Noble-metal-free BODIPY-cobaloxime photocatalysts for visible-light-driven hydrogen production.

In this study a series of supramolecular BODIPY-cobaloxime systems Co-Bn (n = 1-4): [{Co(dmgH)2Cl}{4,4-difluoro-8-(4-pyridyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene}] (Co-B1), [{Co(dmgH)2Cl}{4,4-difluoro-8-(4-pyridyl)-1,3,5,7-tetramethyl-2,6-diiodo-4-bora-3a,4a-diaza-s-indacene}] (Co-B2), [{Co(dmgH)2Cl}{4,4-difluoro-8-(3-pyridyl)-1,3,5,7-tetramethyl-4-bora-3a,4a-diaza-s-indacene}] (Co-B3), and [{Co(dmgH)2Cl}{4,4-difluoro-8-(3-pyridyl)-1,3,5,7-tetramethyl-2,6-diiodo-4-bora-3a,4a-diaza-s-indacene}] (Co-B4) (BODIPY = boron dipyrromethene, dmgH = dimethylglyoxime) have been synthesized by replacing one axial chlorine of cobaloxime moieties with the pyridine residues of BODIPYs, and structurally characterized. Absorption spectra show that the optical properties of the BODIPY-cobaloximes are essentially the sum of their constituent components, indicating weak interactions between the cobaloxime units and BODIPY chromophores in the ground state. If any, electronic communications may take place through the intramolecular electron transfer across their orthogonal structures. The possibility of intramolecular electron transfer is further supported by the results of the density functional theory (DFT) calculations at UB3LYP/LANL2DZ levels on Co-B2˙(-) and Co-B4˙(-), which show that the highest occupied molecular orbitals (HOMOs) possess predominantly BODIPY character, while the lowest unoccupied molecular orbitals (LUMOs) are located on the cobalt centers. The HOMO → LUMO transition is an electron-transfer process (BODIPY˙(-) radical anions → cobaloxime fragments). In view of the possible occurrence of electron transfer, these noble-metal-free BODIPY-cobaloximes are studied as single-component homogeneous photocatalysts for H2 generation in aqueous media. Under optimized conditions, the 2,6-diiodo BODIPY-sensitized cobaloxime Co-B4 that contains a meta-pyridyl at the 8-position of BODIPY presents excellent H2 photoproduction catalytic activity with a turnover number (TON) of 85, which is comparable to that of its analogue Co-B2 that has a para-pyridyl attached onto 2,6-diiodo BODIPY (TON = 82); however, both of the noniodinated BODIPY-sensitizer cobaloximes (Co-B1, Co-B3) exhibit a complete lack of activity under the same experimental conditions. These results show that the presence of heavy atoms in the core of BODIPY is essential for the catalytic process and reductive quenching pathways (namely, the intramolecular electron transfers from BODIPY˙(-) species to the cobalt centers) for these photocatalytically active systems of Co-Bn (n = 2 and 4) are thermodynamically feasible for the hydrogen-evolving reaction.

Experimental and theoretical study of enol-keto prototropic tautomerism and photophysics of azomethine-BODIPY dyads.

In this study we report about two novel azomethine­BODIPY dyads 1 and 2. The two dyads have been, respectively, synthesized by covalent tethering of tautomeric ortho-hydroxy aromatic azomethine moieties including N-salicylideneaniline (SA) and N-naphthlideneaniline (NA) to a BODIPY fluorophore. Both of the two dyads 1 and 2 show enol-imine (OH) structures dominating in the crystalline state. Dyad 1 in the enol state is the most stable form at room temperature in most media, while enol­keto prototropic tautomerism of the NA moiety in solution is preserved in dyad 2, which can be reversibly converted between enol and keto forms in the environment's polarity. Visible illumination of dyad 2 in the enol state excites selectively the BODIPY fragment and then deactivates radiatively by emitting green light in the form of fluorescence, while the emission intensity of 2 in the keto state is quenched on the basis of the proton-coupled photoinduced electron transfer (PCPET) mechanism. This allows large fluorescence modulation between the two states of dyad 2 and generates a novel tautomerisable fluorescent switch. Theoretical calculations including calculated energies, potential energy surfaces (PESs) and intrinsic reaction coordinate (IRC) analysis further support that the single proton transfer reaction from an enol form to a transition state (TS) and from the TS to a keto form for 2 is easier to occur than that for 1, which accounts for the fluorescence quenching of 2 in methanol. The agreement of the experimental results and theoretical calculations clearly suggests that fluorescent and tautomeric components can be paired within the same molecular skeleton and the proton tautomerization of the latter can be designed to regulate the emission of the former. In addition, preliminary experiments revealed that 1 can be potentially used as a simple on/off fluorescent chemosensor which exhibited higher selectivity for Cu(2+) over other common cations.

A simple BODIPY-aniline-based fluorescent chemosensor as multiple logic operations for the detection of pH and CO2 gas.

A simple 4-aniline boron-dipyrromethene (BODIPY) dye (1) was developed as a highly sensitive acidic pH fluorescent probe excitable with visible light based on a photoinduced electron transfer (PeT) mechanism. The pH titration indicates that the fluorescence intensity increases more than 500-fold within the pH range of 4.12-1.42 with a pKa value of 3.24 in methanol-water (1 : 1, v/v) solution, which is valuable for studying strongly acidic conditions. Density functional theory (DFT) calculations reproduce the fluorescence off-on behavior. 1 has also been used as a fluorescent chemosensor for the visual detection of dissolved carbon dioxide (CO2) gas. The underlying mechanism of the sensing process is rationalized. This probe can be recovered by bubbling nitrogen (N2) gas into CO2-treated solutions for over 10 cycles. In addition, two logic gates (OR and INH) have been achieved at the molecular level by changing the initial states of system 1 and chemical inputs.