Tin Derivative Research Articles

Many-Exciton Quantum Dynamics in a Ruddlesden-Popper Tin Iodide.

We present a study on the many-body exciton interactions in a Ruddlesden-Popper tin halide, namely, (PEA)2SnI4 (PEA = phenylethylammonium), using coherent two-dimensional electronic spectroscopy. The optical dephasing times of the third-order polarization observed in these systems are determined by exciton many-body interactions and lattice fluctuations. We investigate the excitation-induced dephasing (EID) and observe a significant reduction of the dephasing time with increasing excitation density as compared to its lead counterpart (PEA)2PbI4, which we have previously reported in a separate publication [J. Chem. Phys.2020, 153, 164706]. Surprisingly, we find that the EID interaction parameter is four orders of magnitude higher in (PEA)2SnI4 than that in (PEA)2PbI4. This increase in the EID rate may be due to exciton localization arising from a more statically disordered lattice in the tin derivative. This is supported by the observation of multiple closely spaced exciton states and the broadening of the linewidth with increasing population time (spectral diffusion), which suggests a static disordered structure relative to the highly dynamic lead-halide. Additionally, we find that the exciton nonlinear coherent lineshape shows evidence of a biexcitonic state with low binding energy (<10 meV) not observed in the lead system. We model the lineshapes based on a stochastic scattering theory that accounts for the interaction with a nonstationary population of dark background excitations. Our study provides evidence of differences in the exciton quantum dynamics between tin- and lead-based Ruddlesden-Popper metal halides (RPMHs) and links them to the exciton-exciton interaction strength and the static disorder aspect of the crystalline structure.

Optimization Process In The Synthesis of Stannous Chloride (SnCl2) by Redox Method In The Context of Downstream Tin Derivative Product

Indonesia has been known as the Tin Island in Southeast Asian Tin Belt region. This makes Indonesia listed as the second biggest tin producer in the world after China, with production reached 33.444 metric tons. However, 95% of tin which has been exported is still in the form of bars, not the optimal downstream tin derivative products, especially in the form of tin chemicals such as SnCl2. It turned out that tin chemical products are imported to meet the needs of domestic industry. In 2014, tin import reached USD 200 million. As one of the downstream products of tin derivatives, SnCl2 can be used as a catalyst, reducing agent, and as the main ingredient for other tin derivative products. This research was conducted based on the demand of industry, PT Timah Industri, to study the synthesis of SnCl2 powder in optimum conditions with redox method. The tin powder was dissolved in concentrated HCl heated on a hotplate, with variations in the particle size of the tin, HCl concentration and the reaction temperature. Differential Thermal Analysis (DTA) was carried out at 8000C with a heating rate of 100Cmin-1. The morphological structure of SnCl2 powder can be determined using 3D-Optical Microscope VHX-5000. As for the SnCl2 phase, it can be identified using the Rigaku SmartLab X-ray diffraction. This attempt has succeeded in synthesizing SnCl2 powder at optimum conditions with a yield percentage of 95%.

N-Heterocyclic Carbene-Stabilized Germanium and Tin Analogues of Heavier Nitriles: Synthesis, Reactivity, and Catalytic Application

The synthesis of stable heavier analogues of nitriles as monomeric tetrylene-phosphinidenes MesTerEP(IDipp) (E = Ge, Sn; MesTer = 2,6-Mes2C6H3, IDipp = C([N-(2,6-iPr2C6H4)CH]2) was achieved by taking advantage of NHC (N-heterocyclic carbene, here IDipp) coordination to the low-valent phosphorus center. Multiple bonding character of the E-P bonds was examined experimentally and computationally. Both germanium and tin compounds undergo [2+2] cycloaddition with diphenylketene, whereas reaction of the tin derivative with tris(pentafluorophenyl)borane provided unique "push-pull" phosphastannene (MesTer)(Ar)Sn = P(IDipp) (Ar = C6F4[B(F)(C6F5)2]). Going further, we demonstrated the potential of tetrylene-phosphinidene complexes in catalytic hydroboration of carbonyl compounds.

Copper (Photo)redox Catalyst for Radical Photopolymerization in Shadowed Areas and Access to Thick and Filled Samples

The free radical polymerization of low viscosity methacrylate blends upon a LED irradiation at 405 nm under air is carried out using Cu(I)/iodonium salt/tin(II) organic derivative as photoinitiating systems. The system exhibits a high reactivity; where tin derivative plays a crucial role. It operates through a catalytic cycle in which Cu(I) is regenerated and can be used at low concentrations (0.1–0.3 wt %). Remarkable performances are achieved. At first, a final methacrylate conversion of 82% after 40 s in 1.4 mm thick samples is obtained for an irradiance of 35 mW/cm2 whereas such a conversion is only reached only when using a Cu(I)/iodonium salt system under a 200 mW/cm2 light exposure. Second, a 55% conversion is still obtained after 150 s under a very low irradiance (2.5 mW/cm2). Third, almost tack-free thick samples (1.4 mm) under air are produced upon sunlight exposure (65% of conversion for the 1.4 mm thick sample after 90 s of irradiation). Fourth, the photocuring of clear samples as thick as 9 c...

Study of Optical and Electrical Properties of Tin-Doped Magnesium Phthalocyanine Thin Films Grown by Thermal Co-Evaporation

The aim of this work is to investigate specific properties of tin-doped magnesium phthalocyanine (Sn-doped MgPc) thin films grown by thermal co-evaporation. Morphological, optical and chemical properties of the doped-films were characterized by atomic force microscopy (AFM), UV-Visible spectroscopy and X-ray photoelectron spectroscopy (XPS). Furthermore, electrical properties of ITO/Sn-doped-MgPc/Al devices such as carrier mobility and carrier concentration were extracted from current-voltage and capacitance-voltage measurements. Morphology of the doped films shows strong dependence on the existence of Sn in the doped films as clearly observed by changing of features of the film surface e.g. surface grain size and roughness. Optical absorption spectra of all conditions provide regular three dominant beta-phase peaks at 352, 640 and 691 nm corresponding to absorption from B-band and Q-band, respectively. The electrical properties obtained from ITO/Sn-doped MgPc/Al device suggest that the enhancement of the current flow in the doped device is a result from the increase of both carrier mobility and carrier concentration. Moreover, photoelectron analysis reveals two formations of Sn dopant in MgPc those are tin metal and derivative of tin oxide.

Multiple Reactivity of SnII Complexes Bearing Catecholate and o‐Amidophenolate Ligands

The reactivity of tin(II) catecholate complex CatSn (1) (where Cat = 3,6‐di‐tert‐butylcatecholate dianion) and two o‐amidophenolate complexes DippAPSn (2) and PhAPSn (3) [where DippAP = 4,6‐di‐tert‐butyl‐N‐(2,6‐diisopropylphenyl)amidophenolate; PhAP = 4,6‐di‐tert‐butyl‐N‐(phenyl)amidophenolate dianions] towards different reagents is reported. Products of the insertion of 1 and 2 into the S–S bond of tetramethylthiuram disulfide were obtained and characterised by X‐ray diffraction analyses. The low temperature oxidation of complexes 1 and 2 with 2‐ethoxy‐3,6‐di‐tert‐butylphenoxy radical enabled us to detect formation of paramagnetic tin(II) derivatives containing the radical‐anion form of the redox‐active ligand. The reaction of tin derivative 3 with Ni(CO)4 leads to substitution of one of the CO groups in the latter with the formation of a new bimetallic product.

First air stable tin(II) β-heteroarylalkenolate: Synthesis, characterization and application in chemical vapor deposition

A novel tin(II)-compound, bis(η 2-N,O-2-[4,5-dimethyloxazolyl]-1,1,1-trifluoro-propen-2-olato)tin, Sn II[(Me 2C 3NO)(CHCOCF 3)] 2 ( 1), was obtained by reacting Sn[N(SiMe 3) 2] 2 with 2 M equivalents of the β-heteroarylalkenol, (Me 2C 3NO)(CHCOHCF 3) ( 2). The molecular structures of ligand and the tin derivative were elucidated by single crystal X-ray diffraction and multi-nuclear NMR spectroscopic studies, which confirmed the monomeric nature and fourfold coordination of the tin(II) center with a pseudo-pyramidal geometry. The bidentate chelating mode of 2 imparted intriguingly high air stability to 1, which together with its high volatility make it an interesting precursor for the chemical vapor deposition (CVD) process. CVD of 1 on gold-coated Al 2O 3 substrates produced single crystalline SnO 2 nanowires by vapor–liquid–solid growth mechanism. Transmission electron microscopy studies and X-ray diffraction data confirmed the high crystallinity of SnO 2 nanowires possessing an average diameter of 90 nm.

Unprecedented Dinuclear Tin Derivative of Deprotonated β-Cyclodextrins

Two unprecedented dinuclear tin compounds containing deprotonated beta-cyclodextrins have been constructed by using different organotin and inorganotin precursors under solvothermal conditions, which display two dinuclear airscrew-like structures with different packing modes.

Synthesis and pyrolysis of silicon and tin containing poly(2,2′-dioxy-1,1′-biphenoxy-phosphazenes)

The polyphosphazene {[NP(O2C12H8)]0.5[NP(OC6H4Br)2]0.5}n (1) [(O2C12H8)=2,2′-dioxy-1,1′-biphenyl] that, as an strictly alternating copolymer, can be considered nearly as the homopolymer [NP(O2C12H8)NP(OC6H4Br)2]n, was reacted first with tBuLi in THF at −78°C to give the intermediate [NP(O2C12H8)NP(OC6H4Li)2]n (2) and subsequently with the chlorosilanes SiMe3Cl and SiMe2(C6H5)Cl or with the chlorostannane SnMe3Cl, to obtain the new polyphosphazenes {(NP[O2C12H8])0.5[NP(OC6H4SiMe3)2]0.5−x[NP(OC6H5)(OC6H4SiMe3)]x}n (3a) (x=0.15–0.5), {(NP[O2C12H8])0.5[N(POC6H4SiMe2Ph)2]0.2[NP(OC6H5)(OC6H4SiMe2Ph)]0.3}n (3b), and {(NP[O2C12H8])0.5[NP(OC6H5)(OC6H4SnMe3)]0.5}n (4), having a very regular distribution of the silicon or tin organometallic sites along the chains. The pyrolysis of the polymers in air at 800°C gave microcrystalline residues (characterized by IR, XRD, SEM and TEM-EDXA) consisting on phases of SiO2·P2O5·P2O7.9·SiP2O7, or, in the case of the tin derivative, almost pure SnP2O7. The results indicate that, while part of the Si content is lost during the pyrolysis, almost all the tin in the original polymer was incorporated to the final residue.

Zur Bildung einer Zinn‐Zinn‐Bindung in Bis(hexamethyldisilazyl)‐Zinn(II) unter C‐H Bindungsbruch

AbstractFormation of a Tin‐Tin‐Bond from Bis(hexamethyldisilazyl)‐Tin(II) under Fission of a C‐H BondBis(hexamethyldisilazyl)tin(II) in excess reacts with the molecular alumosiloxane (Ph2SiO)8(AlO(OH))4 to yield the well known tin(II) derivative (Ph2SiO)8(AlO2)4Sn2 and the novel bicyclic [(Me3Si)2N]Sn[N(SiMe3)SiMe2CH2]2Sn[N(SiMe3)2] containing a tin‐tin bond, which is formally related to the starting molecule by a missing hydrogen atom. From X‐ray diffraction studies on single crystals it follows that the new compound has almost C2 point symmetry (the twofold axis intersecting the tin‐tin bond) and that this tin‐tin bond is the fusion edge of anellated fivefold Sn‐Sn‐N‐Si‐C rings. The bond connecting the almost tetrahedrally coordinated tin atoms (2.737(2) Å) is astonishingly very short. This feature is also reflected in the spectroscopic data (1H, 13C, 29Si, 119Sn‐NMR) of the compound with a coupling constant 1J (117Sn/119Sn) of 9529 Hz.

Products of hydrolysis of C, N-chelated triorganotin(IV) chlorides and use of products as catalysts in transesterification reactions

Triorganotin(IV) chlorides containing one L CN chelating ligand were hydrolyzed with an excess of sodium hydroxide. The composition of the products is strongly dependent on the nature of the organic groups bound to the tin atom. Di( n-butyl)tin, dimethyltin as well as the diphenyl derivative exhibits an equilibrium between hydroxide and stannoxane forms (oxide), whereas alkyltin species react spontaneously and reversibly with carbon dioxide present in the air to form carbonate species. On the other hand, diphenyl derivatives display virtually no reaction with CO 2 towards carbonates, while the di- t-butyl-substituted tin derivative is stable under the same experimental condition and remains as a tin hydroxide. In the case of the dimethyltin derivative, a methyl group migration was observed with displacement of one L CN chelating ligand during the reaction on the air. The coordination geometry of the tin central atom(s) of all studied compounds can be described as trigonal bipyramidal with a dative bonded dimethylamino group occupying one coordination site. The catalytic activity of these compounds in transesterification reactions is generally lower compared to the systems reported in the literature, with the exception of the transesterification of ethyl acetate by cyclohexanol which displays a remarkable activity.

New stable germylenes, stannylenes, and related compounds. 8. Amidogermanium(II) and ‐tin(II) chlorides R2N‐E14‐Cl (E14 = Ge, R = Et; E14 = Sn, R = Me) revealing new structural motifs

AbstractNew stable amidogermanium(II) and ‐tin(II) chlorides R2NE14Cl [E14 = Ge, R = Et (1), E14 = Sn, R = Me (2)] have been synthesized and their crystal structures have been determined by X‐ray diffraction analysis. Both 1 and 2 are dimers formed via the two intermolecular E14← N dative interactions, with the bridged amido ligands and the terminal chloro ligands. The central E142N2 four‐membered ring has a butterfly conformation in the germanium derivative 1 and a planar conformation in the tin derivative 2. The chloride atoms are disposed in the trans‐configuration relative to the four‐membered ring. Both structures 1 and 2 reveal new previously unobserved structural motifs for amidogermanium(II) and ‐tin(II) chlorides, respectively. The electronic structures of 1 and 2 were studied by quantum chemistry within the DFT approach. Copyright © 2007 John Wiley &amp; Sons, Ltd.

Photophysical Properties of a Rhodium Tetraphenylporphyrin-tin Corrole Dyad. The First Example of a Through Metal–Metal Bond Energy Transfer†

The luminescence spectroscopy study and the determination of the photophysical parameters for the M-M'-bonded rhodium meso-tetraphenylporphyrin-tin(2,3,7,13,17,18-hexamethyl-8,12-diethylcorrole) complex, (TPP)Rh-Sn(Me6Et2Cor) 1, was investigated. The emission bands as well as the lifetimes (tau(e)) and the quantum yields (Phi(e); at 77 K using 2MeTHF as solvent) were compared with those of (TPP)RhI 2 (TPP = tetraphenylporphyrin) and (Me6Et2Cor)SnCl 3 (Me6Et2Cor = 2,3,7,13,17,18-hexamethyl-8,12-diethylcorrole) which are the two chemical precursors of 1. The energy diagram has been established from the absorption, fluorescence and phosphorescence spectra. The Rh(TPP) and Sn(Me6Et2Cor) chromophores are the energy donor (D) and acceptor (A), respectively. The total absence of fluorescence in 1 (while fluorescence is observed in the tin derivative 3) indicates efficient excited state deactivation, presumably due to heavy atom effect and intramolecular energy transfer (ET). The large decreases in tau(P) and Phi(P) of the Rh(TPP) chromophore going from 2 to 1 indicate a significant intramolecular ET in the triplet states of 1 with an estimated rate ranging between 10(6) and 10(8) s(-1). Based on the comparison of transfer rates with other related dyads that exhibit similar D-A separations and no M-M' bond, and for which slower through space ET processes (10(2)-10(3) s(-1)) operate, a through M-M' bond ET has been unambiguously assigned to 1.

Inorganic−Organic Hybrids of the p,p‘-Diphenylmethylenediphosphinate, pcp2-. Synthesis, Characterization, and XRPD Structures of [Sn(pcp)] and [Cu(pcp)

Two new inorganic-organic polymeric hybrids [Sn(pcp)] and [Cu(pcp)], pcp=CH2(PhPO2)2(2-), have been synthesized and structurally characterized. The tin derivative has been obtained by reaction of the p,p'-diphenylmethylenediphosphinic acid (H2pcp) in water with SnCl2.2H2O, while the copper derivative has been synthesized through a hydrothermal reaction from the same H2pcp acid and Cu(O2CMe)2.H2O. The structures of these compounds have been solved "ab initio" by X-ray powder diffraction (XRPD) data. [Sn(pcp)] has a ladder-like polymeric structure, with tin(II) centers bridged by diphenylmethylenediphosphinate ligands, and alternating six- and eight-membered rings. The hemilectic coordination around the metal shows the tin(II) lone pair to be operative, resulting in significant interaction mainly with a C-C bond of one phenyl ring. The [Cu(pcp)] complex displays a polymeric columnar structure formed by two intersecting sinusoidal ribbons of copper(II) ions bridged by the bifunctional phosphinate ligands. The intersections of the ribbons are made of dimeric units of pentacoordinated copper ions. Crystal data for [Sn(pcp)]: monoclinic, space group P2(1)/c, a=11.2851(1), b=15.4495(6), c=8.6830(1) A, beta=107.546(1) degrees, V=1443.44(9) A, Z=4. Crystal data for [Cu(pcp)]: triclinic, space group P, a=10.7126(4), b=13.0719(4), c=4.9272(3) A, alpha=92.067(5), beta=95.902(7), gamma=87.847(4) degrees, V=685.47(7), Z=2. The tin compound has been characterized by 119Sn MAS NMR (magic-angle spinning NMR), revealing asymmetry in the valence electron cloud about tin. Low-temperature magnetic measurements of the copper compound have indicated the presence of weak antiferromagnetic interactions below 50 K.

Synthesis and structure of octahedral bis-chelate Tin(IV) derivative of the ruthenocene series

Cyclopalladated α-(p-tolylimino)benzylruthenocene reacts with metallic tin in a way similar to ferrocene analogs, yielding bis-chelate diruthenocenyl tin(IV) compound as a result of transmetalation.

Compounds of Germanium, Tin, and Lead Containing the Ligand C(SiMe3)2(SiMe2C5H4N-2)

Reactions between LiC(SiMe3)(2)(SiMe2C5H4N-2), 1, and the halides GeCl2.dioxane, SnCl2, and PbCl2 gave the isostructural compounds MCl{C(SiMe3)(2)(SiMe2C5H4N-2)} (M = Ge, 2; Sn, 3; or Pb, 4) which contain three-coordinate M. Treatment of the tin derivative 3 with MeI gave the oxidative addition product SnMeClI{C(SiMe3)(2)(SiMe2C5H4N-2)}, 51 and this reacted with AgOCOCF3 or AgOSO2C6H4Me-4 to give, respectively, the compounds SnMeX2{C(SiMe3)(2)(SiMe2C5H4N-2)} with X = OCOCF3, 6, or OSO2C6H4Me-4, 7. Despite the presence of the bulky C(SiMe3)(2)(SiMe3C5H4N-2) ligand, the Sn atom in the solid state structures of 6 and 7 is five-coordinate, and multinuclear NMR studies show that five-coordinate species are present also in THF solutions of 5, 6, and 7.

On the behaviour of organotin compounds with cyclodextrins: Part 1. The complex between allyl-di- n-butyltin chloride and β-cyclodextrin

A complex between allyl-di- n-butyltin chloride and β-cyclodextrin has been obtained in good yield by the coprecipitation method in aqueous solution at room temperature. The stoichiometry, determined by NMR and elemental analysis, was found to be 1:1. The complex was characterised by means of several techniques, such as TGA, DSC, ESIMS, SEM, NMR, and Mössbauer spectroscopy. On the basis of these results, we suggest a structure for this complex where the tin derivative is included in the cyclodextrin, replacing about six of the ca. nine water molecules coordinated to it and where the metal centre displays a pentacoordination, probably due to Sn⋯O long range contacts with the hydroxyl groups of the rim of the macrocycle.

The cyclotrimerisation of (+)-camphor

Naturally occurring (+)-camphor was converted into 2-bromobornene and metallated at the 3-position by lithium and trimethyltin. The latter tin derivative, treated with Cu(NO 3) 2·3H 2O in THF affords the syn and anti cyclotrimers plus a number of byproducts. The rather unexpected formation of the anti stereoisomer plus the structure of several byproducts confirm a mechanistic proposal based on a SnSn coupling process.

The asymmetric synthesis of phosphorus- and sulfur-containing tricarbonyl(η6-arene)chromium complexes using the chiral base approach

The use of a simple chiral lithium amide base 2 enables the asymmetric transformation of tricarbonyl[η6-(diphenylphosphinoyl)benzene]chromium(0) 12 into the corresponding ortho-silylated complex in up to 86% ee. A tin derivative was prepared similarly and was then used to prepare other derivatives via reduction to the corresponding phosphine, followed by transmetallation–electrophilic quench. In the case of tricarbonyl(η6-1,3-dihydroisobenzothiophene)chromium(0) the chiral base 2 was ineffective, and it was necessary to use a bis-lithium amide base 9 to effect asymmetric substitution in high ee (up to 95%). Decomplexation gave the corresponding chiral sulfides in highly enantiomerically enriched form. In all cases the absolute stereochemistry of the products was derived by conducting X-ray structure determinations on selected examples.

Divalent tin and lead complexes of a bulky salen ligand: the syntheses and structures of [SalenBut,Me]Sn and [SalenBut,Me]Pb

The divalent tin and lead complexes, [SalenBut,Me]Sn and [SalenBut,Me]Pb, have been synthesized by the reactions of [(Me3Si)2N]2M (M = Sn, Pb) with the substituted Salen compound, [SalenBut,Me]H2. [SalenBut,Me]Sn and [SalenBut,Me]Pb have been characterized by X-ray diffraction, which demonstrates that the complexes are structurally similar, with the metal atom located above the [N2O2] plane. Despite their similar structures, however, 1H NMR spectroscopy demonstrates that the barrier for the formal transfer of the metal from one face of the ligand to the other is significantly greater for the tin derivative.