QCW surface-pumped cryogenically cooled single-slab laser with 1 kW level at 946 nm.

We present a kilowatt-level quasi-continuous-wave (QCW) cryogenically cooled 946-nm slab laser oscillator for the first time, to the best of our knowledge. The laser system is based on a double-face-pumped large-size single-slab Nd:YAG design, delivering a record-high average power of 1.06 kW without additional amplification. This laser oscillator operates at repetition rate of 400 Hz with a pulse duration of 175 µs, resulting in a single pulse energy of 2.65 J. To the best of our knowledge, these results represent the highest output power and pulse energy for any all-solid-state 946-nm laser ever reported to date. Our scheme paves a new path for the development of the compact high-power solid-state 946-nm laser.

Two Unexpected Temperature-Induced Supermolecular Isomers from Multi-Topic Carboxylic Acid: Hydrogen Bonding Layer or Helix Tube.

Under ambient conditions or 160 °C, two supramolecular isomers, namely [(H4PTTA)(H2O)2(DMF)] and [(H4PTTA)(H2O)3]··Guest (1-L and 1-H, H4PTTA = N-phenyl-N'-phenyl bicyclo[2.2.2]oct-7-ene-2,3,5,6-tetracarboxdiimide tetra-carboxylic acid, Guest = DMF and H2O), were obtained through the reaction of H4PTTA in a mixture of H2O and dimethylformamide. The single crystal structures reveal the temperature-dependent supramolecular isomerism derived from the torsion of semi-rigid of H4PTTA. The 1-L prepared at room temperature is a hydrogen bond based achiral layer, while the hydrothermal synthesized 1-H is isomer resulted in an H-bond-based chiral tubes-packed supramolecular framework.

Void-free bonding for a large slab laser crystal.

A void-free bonding technique was demonstrated for a large slab Nd: YAG crystal with a bonding surface dimension of ∼160mm×70mm. By using the novel fluxless oxide layer removal technology, the indium-oxide barrier problem was resolved. With the help of electrochemical-polished indium solder and a plasma-cleaned heat sink, the solderability of the indium was enhanced; in particular, the contact angle of the solder was improved from 51° to 31°. With the largest-bonding-size slab, a single-slab laser created a maximum output power of 7.3 kW under an absorbed pump power of 12.8 kW, corresponding to an optical to optical efficiency of 57% and a slope conversion of 67.8%. By detecting the wavefront of the interferometer before and after bonding, the RMS of wavefront was 0.192λ and 0.434λ (λ=633nm), respectively. To the best of our knowledge, this is the largest void-free bonding size for a laser slab and the highest output power achieved from a single-slab crystal laser oscillator.

8.2 kW high beam quality quasi-continuous-wave face-pumped Nd:YAG slab amplifier.

An 8 kW level quasi-continuous-wave (QCW) face-pumped 1064 nm slab laser with high beam quality was developed by a master oscillator power amplifier (MOPA) system. A single-mode fiber seed laser was amplified by two-stage single-pass Nd:YAG rod preamplifiers and four face-pumped Nd:YAG slab amplifiers. The slab amplifiers were well designed with uniform pumping and uniform cooling for well-distributed thermal and stress. A dynamically feedbacked optical aberration compensation device was employed to correct low-order optical aberration, and the residue high-order optical aberration was corrected by an adaptive optics system. The QCW MOPA delivered up to an average power of 8.2 kW with a pulse duration of 200 µs at a repetition rate of 400 Hz. The beam quality factor was measured to be ß=3.5.

A zeolite-like zinc triazolate framework with high gas adsorption and separation performance.

The reaction of commercially available 3-amino-1,2,4-triazole (Hatz) and Zn(OH)(2) at room temperature produced a porous zeolite-like metal azolate framework, [Zn(atz)(2)] (MAF-66). Single-crystal X-ray diffraction studies of MAF-66 showed that atz(-) served as an imidazolate-type ligand, linking tetrahedral Zn(II) ions to form a noninterpenetrated dia framework, which contains a narrow, three-dimensional intersecting channel system (void = 49.8%) functionalized by amino groups and uncoordinated triazolate N atoms on the pore surface. Gas-sorption measurements of MAF-66 revealed high CO(2) uptakes (27.6/19.4 wt % at 273/298 K and 1 atm) and high Henry's law CO(2)/N(2) selectivity (403/225 at 273/298 K). The host-guest interactions between CO(2) and the pore surface were also studied by in situ IR absorption spectroscopy and powder X-ray diffraction measurements.

Pentanuclear and heptanuclear helicates by self-assembly of d10 metal ions and a rigid aromatic bis-bidentate chelator.

The self-assembly of Zn(II) and Cd(II) ions with a bis-bidentate ligand 3,5-bis(benzimidazol-2-yl)pyrazole (H 3L) was studied by Electrospray ionization mass spectrometry, (1)H NMR measurements, and single-crystal X-ray diffraction analyses. Reaction of Zn(ClO 4) 2.6H 2O and Cd(ClO 4) 2.6H 2O with H 3L in DMF gave two pentanuclear complexes [(Zn 5(mu 3-O)(H 2L) 6)(ClO 4) 2.DMF.9.5H 2O ( 1) and [Cd 5(mu 3-O)(H 2L) 6](ClO 4)(OH).4.75DMF.0.25EtOH.10.5H 2O ( 2), in which the trigonal-bipyramidal core structures are bridged by mu 3-oxo and pyrazolate rings of the monodeprotonated H 2L. When Na 3PO 4.12H 2O was used in the reaction system of CdBr 2.4H 2O and H 3L, [Cd 5(mu 3-O)(H 2L) 6]Br 2.4.5DMF.6.5H 2O ( 3) and [Cd 7(mu 6-PO 4)(mu-Br) 3(H 2L) 6](HPO 4).DMF.10H 2O ( 4) were isolated. 3 displays the same core structure as that of 2, whereas 4 exhibits a turbinate, heptanuclear core which is bridged by a mu 6-PO 4, three mu-Br, and three pyrazolate rings. All of the pentanuclear and heptanuclear cores are surrounded by three pairs of bis-bidentate H 2L (-) ligands with offset pi-pi stacking, showing propeller-like molecular structures and triple-stand helicates. Electrospray ionization mass spectrometry studies and (1)H NMR measurements demonstrate that the pentanuclear complexes have different stability in the solution, depending on the metal ions and the counteranions. Furthermore, both 1 and 2 emit blue fluorescence with nanosecond luminescent lifetimes in DMF at room temperature.

Porous metal-organic framework based on mu4-oxo tetrazinc clusters: sorption and guest-dependent luminescent properties.

A three-dimensional, highly porous metal-organic framework [Zn 4O(bdc)(bpz) 2].4DMF.6H 2O ( 1) (bdc = 1,4-benzenedicarboxylate, bpz = 3,3',5,5'-tetramethyl-4,4'-bipyrazolate) constructed by Zn 4O clusters with bdc and bpz linkers, has been prepared and structurally characterized. The N 2 sorption measurements reveal that 1 exhibits high porosity with a Langmuir surface area of 1908 m (2)/g and a pore volume of 0.58 cm (3)/g. Compound 1 features hydrophobic channels with a free passage of approximately 8.2 A defined by the methyl groups from bpz, and it exhibits nice sorption capability for benzene and toluene and interesting two-step sorption behavior for methanol. Meanwhile, 1 also exhibits interesting guest-dependent luminescent properties.

Cleavage of double-strand DNA by zinc complexes of dicationic 2,2'-dipyridyl derivatives.

Two highly charged zinc complexes, [Zn(L1)3](ClO4)8.4H2O (1) and [Zn(L2)2Br](ClO4)5.H2O (2) (L1 = 5,5'-di(1-(triethylammonio)methyl)-2,2'-dipyridyl and L2= 5,5'-di(1-(tributylammonio)methyl)-2,2'-dipyridyl) were synthesized and structurally characterized by crystallography. The zinc atom in 1 shows a distorted octahedral sphere. Variable-pH NMR studies on 1 demonstrated that the saturated six-coordinated [Zn(L1)3]8+ species can partially change into five-coordinated [Zn(L1)2(H2O)]6+ species in aqueous solution. The zinc atom in 2 shows a distorted trigonal-bipyramidal sphere. The average distance of the coordinated Br atom to the cationic N atom in 2 is ca 5.9 A, which is comparable to that of adjacent phosphodiesters in the DNA (ca. 6 A). Both complexes exhibited high nuclease activities towards cleavage of supercoiled plasmid DNA with the activity being the maximum under physiological pH. The effective DNA cleavage may be attributed to the strong electrostatic interaction of the metal moiety and two positive pendants with phosphodiester groups of nucleic acid.

Supramolecular isomerism within three-dimensional 3-connected nets: unusual synthesis and characterization of trimorphic copper(I) 3,5-dimethyl-1,2,4-triazolate.

Solvothermal treatments of acetonitrile, aqueous ammonia and copper(II) salts frequently yielded alpha-[Cu(mtz)](1)(Hmtz = 3,5-dimethyl-1,2,4-triazole) under different reaction conditions. However, two new supramolecular isomers of 1, namely beta-[Cu(mtz)](2) and gamma-[Cu(mtz)](3) were successfully isolated upon introducing 4,4'-bipyridine or nitrate as an additive. 1-3 represent the first example of true supramolecular isomerism within 3D 3-connected nets. Besides the 4.8.10 net for the tetragonal phase 1 (P4(2)/n, a= 13.470(2), c= 6.142(2)A), two novel 3-connected nets, 8(2)10-a and 6.10(2), were observed in the new tetragonal phase 2 (I42d, a= 14.0247(5), c= 5.2884(4)A) and orthorhombic phase 3 (Iba2, a= 8.0423(7), b= 11.5310(10), c= 17.3505(16)A), respectively. The three isomers also displayed distinct physical properties related to their different supramolecular structures.

Temperature- or guest-induced drastic single-crystal-to-single-crystal transformations of a nanoporous coordination polymer.

Aside from a temperature-induced structural transformation, a new nanoporous coordination polymer [Ag6Cl(atz)4].OH.6H2O (Hatz = 3-amino-1,2,4,-triazole) comprised of interpenetrated Ag3(atz)2 coordination nets exhibits a single-crystal-to-single-crystal transformation of a 5-fold to 6-fold net interpenetration change triggered by guest desorption/absorption.

Copper(I) 1,2,4-triazolates and related complexes: studies of the solvothermal ligand reactions, network topologies, and photoluminescence properties.

One-pot solvothermal treatments of organonitriles, ammonia, and Cu(II) salts yielded Cu(I) and 3,5-disubstituted 1,2,4-triazolates. The organic triazolate components were derived from copper-mediated oxidative cycloaddition of nitriles and ammonia, in which a key intermediate 1,3,5-triazapentadienate was isolated as [Cu(II)(4-pytap)(2)] (4-Hpytap = 2,4-di(4-pyridyl)-1,3,5-triazapentadiene) via controlled solvothermal conditions. This intermediate could also be synthesized by Ni(II)-mediated reactions; however, the final triazoles were obtained only when Cu(II) was employed. Therefore, the reaction mechanism of these reactions was elucidated as follows: nitrile was first attacked by ammonia to form the amidine, which further reacted with another nitrile or self-condensed to yield 1,3,5-triazapentadiene, which was coordinated to two Cu(II) ions in its deprotonated form. A two-electron oxidation of the 1,3,5-triazapentadienate mediated by two Cu(II) ions gave one triazolate and Cu(I) cations. Other in situ ligand reactions, such as C-C bond cleavage and hydrolysis, were also found for the nitriles under these solvothermal conditions. Another remarkable feature of these crystalline Cu(I) triazolates is their simple, typical 3- or 4-connected network topologies. The self-assembly of these nets is presumably controlled by steric hindrance, which is subsequently applied to the rational design of the close-packed 2D networks [Cu(I)(tz)](infinity) and [Ag(I)(tz)](infinity) (Htz = 1,2,4-triazole), as well as the porous 3D network [Cu(I)(etz)](infinity) (Hetz = 3,5-diethyl-1,2,4-triazole). The interesting photoluminescence properties of these coinage d(10) metal complexes were also investigated.

Well-resolved, new water morphologies obtained by modification of the hydrophilic/hydrophobic character and shapes of the supporting layers.

The planar coordination complexes [Ag2L2] (L = ophen or obpy, where Hophen = 1H-[1,10]phenanthrolin-2-one and Hobpy = 1H-[2,2']bipyridinyl-6-one) contain both hydrophilic and hydrophobic functional groups. Crystallization of these structurally related complexes in an aqueous medium gives [Ag2(ophen)2]2 x 6H2O (1), [Ag2(obpy)2]3 x 18H2O (2), and [Ag2(obpy)2]2 x 14.5H2O (3). Novel water morphologies are observed in these crystalline hydrates, similar 2D metal-organic layers in which the planar [Ag2L2] complexes as building blocks are stacked alternately together and provide hydrogen bond acceptor sites (O atoms) for anchoring 1D water chains or 2D water layers on their surfaces. In the wavelike metal-organic framework of 1, the wide hydrophobic region renders the formation of 1D water tapes containing four- and six-membered water rings, whereas more complex 2D water layers are sandwiched in 2 and 3, owing to the fact that the surfaces of the supporting layers are more hydrophilic than 1.

Triple-stranded helices and zigzag chains of copper(I) 2-ethylimidazolate: solvent polarity-induced supramolecular isomerism.

The solvent effect of different polarities in hydro(solvo)thermal reaction of Cu(II) and 2-ethylimidazole leads to the generation of two supramolecular isomers of triple-stranded helical and zigzag chain-like structures of Cu(I) 2-ethylimidazolate.

Molecular chairs, zippers, zigzag and helical chains: chemical enumeration of supramolecular isomerism based on a predesigned metal-organic building-block.

A predesigned metal-organic building-block [Cu(I)(2-pytz)](2-Hpytz = 3,5-di-2-pyridyl-1,2,4-triazole) has been successfully used to synthesize four genuine supramolecular isomers.

Metallophilicity versus pi-pi interactions: ligand-unsupported argentophilicity/cuprophilicity in oligomers-of-dimers [M2L2]n (M=CuI or AgI, L=tridentate ligand).

To verify whether attractive metallophilic interactions exist in the dimer-of-dimers [Cu(2)(ophen)(2)](2) (Hophen=1H-[1,10]phenanthrolin-2-one) (1), we designed and synthesized a series of such [M(2)L(2)](2) structures by varying the d(10) metal and/or the ligand (M=Cu(I) or Ag(I), L=ophen or obpy; Hobpy=1H-[2,2']bipyridinyl-6-one), and have successfully obtained three dimers-of-dimers: [Ag(2)(ophen)(2)](2).6 H(2)O (2), [Cu(2)(obpy)(2)](2) (3), and [Ag(2)(obpy)(2)](2).4.5 H(2)O.0.5 DMF (4). X-ray analyses of these structures show that interdimer M-M separations in [Ag(2)-(ophen)(2)](2) (3.199 A) are remarkably shorter than those in [Cu(2)(ophen)(2)](2) (3.595 A). Shorter interdimer M-M separations are found in the structures of [M(2)(obpy)(2)](2) (2.986 and 2.993 A in [Cu(2)(obpy)(2)](2), 3.037 to 3.093 A in [Ag(2)(obpy)(2)](2)), in which the pi systems are smaller than in the complexes with the ophen ligand. Detailed structural comparison of these dimers-of-dimers indicates that the interdimer, face-to-face pi-pi interactions repulse rather than support the interdimer metal-metal attractive interactions. This study also yields qualitative comparison of the strengths between argentophilic, cuprophilic, and face-to-face pi-pi interactions. DFT calculations on the four dimers-of-dimers further support the above deduction. The structure of a trimer-of-dimers [Ag(2)(obpy)(2)](3) (Ag-Ag 3.171 to 3.274 A) is further evidence that the oligomerization of the [M(2)L(2)] molecules is favored by stronger metallophilic and weaker face-to-face pi-pi interactions.

Two mixed-valence copper(I,II) imidazolate coordination polymers: metal-valence tuning approach for new topological structures.

A new metal-valence tuning synthetic approach has been utilized to generate two new mixed-valence Cu(I,II) coordination polymers Cu(2)(im)(3) and Cu(3)(im)(4)(Him = imidazole), which are an unprecedented uninodal 4-connected 4.8(5) topological net and a 4-connected (4,4) net, respectively.