A π‐Conjugation Extended Viologen as a Two‐Electron Storage Anolyte for Total Organic Aqueous Redox Flow Batteries

Extending the conjugation of viologen by a planar thiazolo[5,4‐d]thiazole (TTz) framework and functionalizing the pyridinium with hydrophilic ammonium groups yielded a highly water‐soluble π‐conjugation extended viologen, 4,4′‐(thiazolo[5,4‐d]thiazole‐2,5‐diyl)bis(1‐(3‐(trimethylammonio)propyl)pyridin‐1‐ium) tetrachloride, [(NPr)₂TTz]Cl₄ , as a novel two‐electron storage anolyte for aqueous organic redox flow battery (AORFB) applications. Its physical and electrochemical properties were systematically investigated. Paired with 4‐trimethylammonium‐TEMPO (N^Me‐TEMPO) as catholyte, [(NPr)₂TTz]Cl₄ enables a 1.44 V AORFB with a theoretical energy density of 53.7 Wh L^?1. A demonstrated [(NPr)₂TTz]Cl₄ /N^Me‐TEMPO AORFB delivered an energy efficiency of 70 % and 99.97 % capacity retention per cycle.     

Spray‐processable thiazolothiazole‐based copolymers with altered donor groups and their electrochromic properties

Two novel thiazolo[5,4‐d]thiazole containing donor–acceptor type alternating copolymers, poly[2‐(5‐(2‐decyl‐2H‐benzo[d][1,2,3]triazol‐4‐yl)thiophen‐2‐yl)‐5‐(thiophen‐2‐yl)thiazolo[5,4‐d]thiazole] (BTzTh) and poly[2‐(5‐(2‐decyl‐2H‐benzo[d][1,2,3]triazol‐4‐yl)furan‐2‐yl)‐5‐(furan‐2‐yl)thiazolo[5,4‐d]thiazole] (BTzFr) were synthesized by Stille coupling polymerization and their electrochemical and electrochromic properties were explored. Electrochemical activities of the spray‐casted polymer films were determined by cyclic voltammetry. To evaluate the effect of thiophene and furan moieties on the optical properties of the copolymers, spectroelectrochemistry studies were performed. To examine the switching abilities, copolymer films were subjected to a double potential step chronoamperometry in their local maximum absorptions. Both thiazolothiazole‐containing copolymers showed multichromic properties with low band‐gap values 1.7 and 1.9 eV for BTzTh and BTzFr, respectively. The decent electrochromical properties together with solution processability make them important candidates for electrochromic applications. © 2013 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2013 , 51, 3901–3906     

Experimental and Computational Studies of a Multi‐Electron Donor–Acceptor Ligand Containing the Thiazolo[5,4‐d]thiazole Core and its Incorporation into a Metal–Organic Framework

A ligand containing the thiazolo[5,4‐d]thiazole (TzTz) core (acceptor) with terminal triarylamine moieties (donors), N,N′‐(thiazolo[5,4‐d]thiazole‐2,5‐diylbis(4,1‐phenylene))bis(N‐(pyridine‐4‐yl)pyridin‐4‐amine ( 1 ), was designed as a donor–acceptor system for incorporation into electronically active metal–organic frameworks (MOFs). The capacity for the ligand to undergo multiple sequential oxidation and reduction processes was examined using UV/Vis‐near‐infrared spectroelectrochemistry (UV/Vis‐NIR SEC) in combination with DFT calculations. The delocalized nature of the highest occupied molecular orbital (HOMO) was found to inhibit charge‐transfer interactions between the terminal triarylamine moieties upon oxidation, whereas radical species localized on the TzTz core were formed upon reduction. Conversion of 1 to diamagnetic 2+ and 4+ species resulted in marked changes in the emission spectra. Incorporation of this highly delocalized multi‐electron donor–acceptor ligand into a new two‐dimensional MOF, [Zn(NO₃)₂( 1 )] ( 2 ), resulted in an inhibition of the oxidation processes, but retention of the reduction capability of 1 . Changes in the electrochemistry of 1 upon integration into 2 are broadly consistent with the geometric and electronic constraints enforced by ligation.     

Preparation of halogenated derivatives of thiazolo[5,4‐d]thiazole via direct electrophilic aromatic substitution

Chlorination and bromination reactions of thiazolo[5,4‐d]thiazole led to the generation of its mono‐ and dihalogenated derivatives. These are the first instances of successful direct electrophilic aromatic substitution in the thiazolo[5,4‐d]thiazole ring system. X‐ray analysis demonstrates that both 2‐bromothiazolo[5,4‐d]‐thiazole and 2,5‐dibromothiazolo[5,4‐d]thiazole are planar structures, with strongly manifested π‐stacking in the solid state. Theoretical analysis of the pyridine‐catalyzed halogenation (MP2/6‐31+G(d) and B3LYP/6‐31+G(d) calculations) reveals that introduction of one halogen actually leads to a slightly enhanced reactivity towards further halogenation. Several halogenation mechanisms have been investigated: 1) The direct C‐halogenation with N‐halopyridine as electrophile; 2) C‐halogenation via intermediate N‐halogenation, and 3) C‐halogenation following an addition ‐ elimination pathway, with intermediate formation of a cyclic halonium ion. The theoretical studies suggest that the direct C‐halogenation is the favored mechanism.     

Synthesis and characterization of thiazolothiazole‐based polymers and their applications in polymer solar cells

A novel series of thiazolothiazole (Tz)‐based copolymers, poly[9,9‐didecylfluorene‐2,7‐diyl‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P1), poly[9,9‐dioctyldibenzosilole‐2,7‐diyl‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P2), and poly[4,4′‐bis(2‐ethylhexyl)‐dithieno[3,2‐b:2′,3′‐d]silole‐alt‐2,5‐bis‐(3‐hexylthiophene‐2‐yl)thiazolo[5,4‐d]thiazole] (P3), were synthesized for the use as donor materials in polymer solar cells (PSCs). The field‐effect carrier mobilities and the optical, electrochemical, and photovoltaic properties of the copolymers were investigated. The results suggest that the donor units in the copolymers significantly influenced the band gap, electronic energy levels, carrier mobilities, and photovoltaic properties of the copolymers. The band gaps of the copolymers were in the range of 1.80–2.14 eV. Under optimized conditions, the Tz‐based polymers showed power conversion efficiencies (PCEs) for the PSCs in the range of 2.23–2.75% under AM 1.5 illumination (100 mW/cm²). Among the three copolymers, P1, which contained a fluorene donor unit, showed a PCE of 2.75% with a short‐circuit current of 8.12 mA/cm², open circuit voltage of 0.86 V, and a fill factor (FF) of 0.39, under AM 1.5 illumination (100 mW/cm²). © 2011 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2011     

Efficient organic photovoltaic cells based on thiazolothiazole and benzodithiophene copolymers with π‐conjugated bridges

New donor–π–acceptor (D–π–A) type conjugated copolymers, poly[(4,8‐bis((2‐hexyldecyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene)‐alt‐(2,5‐bis(4‐octylthiophen‐2‐yl)thiazolo[5,4‐d]thiazole)] (PBDT‐tTz), and poly[(4,8‐bis((2‐hexyldecyl)oxy)benzo[1,2‐b:4,5‐b′]dithiophene)‐alt‐(2,5‐bis(6‐octylthieno[3,2‐b]thiophen‐2‐yl)thiazolo[5,4‐d]thiazole)] (PBDT‐ttTz) were synthesized and characterized with the aim of investigating their potential applicability to organic photovoltaic active materials. While copolymer PBDT‐tTz showed a zigzagged non‐linear structure by thiophene π‐bridges, PBDT‐ttTz had a linear molecular structure with thieno[3,2‐b]thiophene π‐bridges. The optical, electrochemical, morphological, and photovoltaic properties of PBDT‐tTz and PBDT‐ttTz were systematically investigated. Furthermore, bulk heterojunction photovoltaic devices were fabricated by using the synthesized polymers as p‐type donors and [6,6]‐phenyl‐C₇₁‐butyric acid methyl ester as an n‐type acceptor. PBDT‐ttTz showed a high power conversion efficiency (PCE) of 5.21% as a result of the extended conjugation arising from the thienothiophene π‐bridges and enhanced molecular ordering in the film state, while PBDT‐tTz showed a relatively lower PCE of 2.92% under AM 1.5 G illumination (100 mW/cm²). © 2018 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2018 , 56, 1978–1988     

Heteroarene‐fused π‐conjugated main‐chain polymers containing 4,7‐bis(4‐octylthiophen‐2‐yl)benzo[c][1,2,5]thiadiazole or 2,5‐bis(4‐octylthiophen‐2‐yl)thiazolo[5,4‐d]thiazole and their application to photovoltaic devices

Two conjugated main‐chain polymers consisting of heteroarene‐fused π‐conjuagted donor moiety alternating with 4,7‐bis(5‐bromo‐4‐octylthiophen‐2‐yl)benzo[c][1,2,5]thiadiazole (P1) or 2,5‐bis(5‐bromo‐4‐octylthiophen‐2‐yl) thiazolo[5,4‐d]thiazole (P2) units have been synthesized. They are intrinsically amorphous in nature and do not exhibit crystalline melting temperatures during thermal analysis. The effect of the fused rings on the thermal, optical, electrochemical, charge transport, and photovoltaic properties of these polymers has been investigated. The polymer (P1) containing 4,7‐bis(5‐bromo‐4‐octylthiophen‐2‐yl)benzo[c][1,2,5] thiadiazole has a broad absorption extending from 300 to 600 nm with optical bandgaps as low as 2.02 eV. The HOMO levels (5.42 to 5.29 eV) are more sensitive to the choice of acceptor. The polymers were employed to fabricate organic photovoltaic cells with methanofullerene [6,6]‐phenyl C71‐butyric acid methyl ester (PC₇₁BM). As a result, the polymer solar cell device containing P1 had the best preliminary results with an open‐circuit voltage of 0.61 V, a short‐circuit current density of 6.19 mA/cm², and a fill factor of 0.32, offering an overall power conversion efficiency of 1.21%. © 2010 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2010     

Regioselectively Synthesis of Thiazolo[4,5‐a]acridines and Oxazolo[5,4‐a]thiazolo[5,4‐j]acridines via Multicomponent Domino Reactions

A regioselective three‐component reaction of aromatic aldehydes, 2‐hydroxy‐1,4‐naphthoquinone and benzo[d]thiazol‐5‐amine in HOAc under microwave irradiation has been developed. A series of new thiazolo‐fused benzo[h]acridines were synthesized with high chemical yields in this one‐pot reaction. The resulting thiazolo‐fused acridines were employed to further react with aldehydes and ammonium acetate to give polycyclic‐fused oxazolo[5,4‐a]thiazolo[5,4‐j]acridines. The present synthesis shows several advantages, such as operational simplicity, fast reaction rates, which makes it a useful and attractive process of library generation for drug discovery.     

Three‐Component Reaction for Construction of Spiro[indoline‐3,7′‐thiazolo[3,2‐a]pyridines] and Spiro[benzo[4,5]thiazolo[3,2‐a]pyridine‐3,3′‐indolines]

The three‐component reaction of thiazole (benzothiazole), dialkyl but‐2‐ynedioate, and isatinylidene malononitriles in toluene at 110–120°C in a sealed tube afforded a mixture of cis/trans‐isomers of functionalized diastereoisomeric spiro[indoline‐3,7′‐thiazolo[3,2‐a]pyridines] and spiro[benzo[4,5]thiazolo[3,2‐a]pyridine‐3,3′‐indolines] in good yields. Both cis‐isomers and trans‐isomers were successfully separated out and fully characterized with spectroscopy and single crystal determination. Under similar conditions, the three‐component reaction containing 2‐(1,3‐dioxo‐1H‐inden‐2(3H)‐ylidene)malononitrile resulted in spiro[indene‐2,7′‐thiazolo[3,2‐a]pyridine] derivatives.     

Synthesis of 2‐amino‐4h‐thiazolo[5,4‐b]indole and characterization of its colored conversion products with protein tyrosine phosphatase inhibitory activity

In DMSO‐solution 2‐amino‐4H‐thiazolo[5,4‐b]indole is converted into a complex mixture of colored products. The three major conversion end‐products, of which two are inhibitors of protein tyrosine phos‐phatases (PTPs), were isolated by chromatographic methods and their structures characterized by spectro‐scopic analysis, including NMR and MS combined with computer assisted structure elucidation, and, finally, confirmed by independent chemical synthesis. Synthesis of 2‐amino‐4H‐thiazolo[5,4‐b]indole as well as its N‐acetyl derivatives prepared from either oxindole or 2‐bromo‐1‐(2‐nitro‐phenyl)ethanone is described.     

Cobalt(II) and cobalt(III) complexes with 4′‐(4‐cyanophenyl)‐2,2′:6′,2′′‐terpyridine

4′‐Cyanophenyl‐2,2′:6′,2′′‐terpyridine (cptpy) was employed as an N,N′,N′′‐tridentate ligand to synthesize the compounds bis[4′‐(4‐cyanophenyl)‐2,2′:6′,2′′‐terpyridine]cobalt(II) bis(tetrafluoridoborate) nitromethane solvate, [Co^II(C₂₂H₁₄N₄)₂](BF₄)₂·CH₃NO₂, (I), and bis[4′‐(4‐cyanophenyl)‐2,2′:6′,2′′‐terpyridine]cobalt(III) tris(tetrafluoridoborate) nitromethane sesquisolvate, [Co^III(C₂₂H₁₄N₄)₂](BF₄)₃·1.5CH₃NO₂, (II). In both complexes, the cobalt ions occupy a distorted octahedral geometry with two cptpy ligands in a meridional configuration. A greater distortion from octahedral geometry is observed in (I), which indicates a different steric consequence of the constrained ligand bite on the Co^II and Co^III ions. The crystal structure of (I) features an interlocked sheet motif, which differs from the one‐dimensional chain packing style present in (II). The lower dimensionality in (II) can be explained by the disturbance caused by the larger number of anions and solvent molecules involved in the crystal structure of (II). All atoms in (I) are on general positions, and the F atoms of one BF₄⁻ anion are disordered. In (II), one B atom is on an inversion center, necessitating disorder of the four attached F atoms, another B atom is on a twofold axis with ordered F atoms, and the C and N atoms of one nitromethane solvent molecule are on a twofold axis, causing disorder of the methyl H atoms. This relatively uncommon study of analogous Co^II and Co^III complexes provides a better understanding of the effects of different oxidation states on coordination geometry and crystal packing.     

Combined experimental–theoretical NMR study on 2,5‐bis(5‐aryl‐3‐hexylthiophen‐2‐yl)‐thiazolo[5,4‐d]thiazole derivatives for printable electronics

Four 2,5‐bis(5‐aryl‐3‐hexylthiophen‐2‐yl)thiazolo[5,4‐d]thiazole derivatives have been synthesized and thoroughly characterized. The extended aromatic core of the molecules was designed to enhance the charge transport characteristics, and solubilizing hexyl side chains were introduced on the thiophene subunits to enable possible integration of these semiconducting small molecules in printable electronics. Complete elucidation of the chemical structures by detailed one‐dimensional/two‐dimensional NMR spectroscopy is described, providing interesting input for chemical shift prediction software as well, because limited experimental data on these types of compounds are currently available. Furthermore, theoretical calculations have assisted experimental observations—giving support for the chemical shift assignment and providing a springboard for future screening and predictions—demonstrating the benefits of a coordinated theoretical–experimental approach. Copyright © 2012 John Wiley & Sons, Ltd.     

A novel one‐dimensional complex: catena‐poly­[[manganese(III)‐di‐μ‐2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolato‐κ2O1,N:κO2;κO2:κ2O1] chloride]

In the title one‐dimensional complex, {[Mn^III(C₉H₁₀NO₂)₂]Cl}_n, the Schiff base ligand 2‐[(2‐hydroxy­ethyl)­imino­methyl]­phenolate (Hsae⁻) functions as both a bridging and a chelating ligand. The Mn^III ion is six‐coordinated by two N and four O atoms from four different Hsae⁻ ligands, yielding a distorted MnO₄N₂ octahedral environment. Each [Mn^III(Hsae)₂]⁺ cationic unit has the Mn atom on an inversion centre and each [Mn^III(Hsae)₂]⁺ cation lies about another inversion centre. The chain‐like complex is further extended into a three‐dimensional network structure through Cl⋯H—O hydrogen bonds and C—H⋯π contacts involving the Hsae⁻ rings.     

A Supramolecular Radical Dimer: High‐Efficiency NIR‐II Photothermal Conversion and Therapy

Photothermal therapy at the NIR‐II biowindow (1000–1350 nm) is drawing increasing interest because of its large penetration depth and maximum permissible exposure. Now, the supramolecular radical dimer, fabricated by N,N′‐dimethylated dipyridinium thiazolo[5,4‐d]thiazole radical cation (MPT^.+) and cucurbit[8]uril (CB[8]), achieves strong absorption at NIR‐II biowindow. The supramolecular radical dimer (2MPT^.+‐CB[8]) showed highly efficient photothermal conversion and improved stability, thus contributing to the strong inhibition on HegG2 cancer cell under 1064 nm irradiation even penetrating through chicken breast tissue. This work provides a novel approach to construct NIR‐II chromophore by tailor‐made assembly of organic radicals. It is anticipated that this study provides a new strategy to achieve NIR‐II photothermal therapy and holds promises in luminescence materials, optoelectronic materials, and also biosensing.     

Novel Pyrano[2,3‐d]thiazole and Thiazolo[4,5‐b]pyridine Derivatives: One‐pot Three‐component Synthesis and Biological Evaluation as Anticancer Agents,c‐Met,and Pim‐1 Kinase Inhibitors

Preparation of pyrano[2,3‐d]thiazole and thiazolo[4,5‐b]pyridine derivatives through multicomponent reactions (MCRs) was achieved by the reaction of 2‐(2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophen‐3‐yl)thiazol‐4(5H)‐one with various active methylene reagents such as ethyl cyanoacetate or malononitrile in basic conditions containing diverse aromatic aldehyde. Furthermore, this study aims to evaluate the in vitro cytotoxic activity of the synthetic compounds against six cancer cell lines, and all the prepared compounds revealed valuable activity compared with the CHS‐828, which is the 2‐[6‐(4‐chlorophenoxy)hexyl]‐1‐cyano‐3‐pyridin‐4‐ylguanidine as the standard drug. Some of the pyrano[2,3‐d]thiazole and thiazolo[4,5‐b]pyridine derivatives showed the highest antitumor activity towards the six cancer cell lines. Moreover, (c‐Met) enzymatic activity of the most potent compounds showed that compounds 3b 2‐(2‐amino‐4,5,6,7 tetrahydrobenzo[b]thiophen‐3‐yl)‐5‐hydroxy‐7‐(2‐hydroxy‐phenyl)‐7H‐pyrano[2,3‐d]thiazole‐6 carbonitrile and 5e 2‐(2‐amino‐4,5,6,7‐tetrahydrobenzo[b]thiophen‐3‐yl)‐5‐hydroxy‐7‐phenyl‐4,7‐dihydrothiazolo[4,5‐b]pyridine‐6‐carbonitrile were with higher activities than foretinib. Three compounds were selected to examine their Pim‐1 kinase where compounds 3b and 7b showed the highest inhibitions.     

Synthesis and Photovoltaic Properties of Cyclopentadithiophene‐Based Low‐Bandgap Copolymers That Contain Electron‐Withdrawing Thiazole Derivatives

We have synthesized four types of cyclopentadithiophene (CDT)‐based low‐bandgap copolymers, poly[{4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl}‐alt‐(2,2′‐bithiazole‐5,5′‐diyl)] ( PehCDT‐BT ), poly[(4,4‐dioctyl‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl)‐alt‐(2,2′‐bithiazole‐5,5′‐diyl)] ( PocCDT‐BT ), poly[{4,4‐bis(2‐ethylhexyl)‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl}‐alt‐{2,5‐di(thiophen‐2‐yl)thiazolo[5,4‐d]thiazole‐5,5′‐diyl}] ( PehCDT‐TZ ), and poly[(4,4‐dioctyl‐4H‐cyclopenta[2,1‐b:3,4‐b′]dithiophene‐2,6‐diyl)‐alt‐{2,5‐di(thiophen‐2‐yl)thiazolo[5,4‐d]thiazole‐5,5′‐diyl}] ( PocCDT‐TZ ), for use in photovoltaic applications. The intramolecular charge‐transfer interaction between the electron‐sufficient CDT unit and electron‐deficient bithiazole (BT) or thiazolothiazole (TZ) units in the polymeric backbone induced a low bandgap and broad absorption that covered 300 nm to 700–800 nm. The optical bandgap was measured to be around 1.9 eV for PehCDT‐BT and PocCDT‐BT , and around 1.8 eV for PehCDT‐TZ and PocCDT‐TZ . Gel permeation chromatography showed that number‐average molecular weights ranged from 8000 to 14 000 g mol^?1. Field‐effect mobility measurements showed hole mobility of 10^?6–10^?4 cm² V^?1 s^?1 for the copolymers. The film morphology of the bulk heterojunction mixtures with [6,6]phenyl‐C₆₁‐butyric acid methyl ester (PCBM) was also examined by atomic force microscopy before and after heat treatment. When the polymers were blended with PCBM, PehCDT‐TZ exhibited the best performance with an open circuit voltage of 0.69 V, short‐circuit current of 7.14 mA cm^?2, and power conversion efficiency of 2.23 % under air mass (AM) 1.5 global (1.5 G) illumination conditions (100 mW cm^?2).     

Modified Riemschneider Reaction of 3‐Thiocyanatoquinolinediones

The Riemschneider reaction of 3‐thiocyanatoquinoline‐2,4(1H,3H)‐diones with conc. H₂SO₄ was investigated. Using different reaction conditions, 13 types of reaction products were isolated. Compounds bearing a Me, Et, or Bu group at C(3) afforded mainly [1,3]thiazolo[5,4‐c]quinoline‐2,4‐diones and 1,9b‐dihydro‐9b‐hydroxythiazolo[5,4‐c]quinoline‐2,4‐diones. In the case of the 3‐Bu derivatives of the starting compounds, C‐debutylation was also observed. If a Bn group is present at C(3), rapid C‐debenzylation of the starting thiocyanates occurred, yielding [1,3]oxathiolo[4,5‐c]quinoline‐2,4‐diones, and mixtures of mono‐, di‐, and trisulfides derived from 4‐hydroxy‐3‐sulfanylquinoline‐2‐ones. The reaction mechanism of all of the transformations is discussed. All new compounds were characterized by IR, ¹H‐ and ¹³C‐NMR, and EI and ESI mass spectra, and in some cases, ¹⁵N‐NMR spectra were also used to characterize new compounds.     

Synthesis of new functionalized imidazo[2,1‐b]thiazoles and thiazolo[3,2‐a]pyrimidines

5‐Oxo‐5H‐[1,3]thiazolo[3,2‐a]pyrimidine‐6‐carboxylic acid ( 4 ), and 6‐methylimidazo[2,1‐b]thiazole‐5‐carboxylic acid ( 17 ) were reacted with amines 6a‐i by the reaction with oxalyl chloride and N, N‐di methyl‐formamide as a catalyst into primary and secondary amide derivatives 7‐14 and 19‐22. From compound 24 N,N'‐disubstituted ureas 26, 27 and perhydroimidazo[1,5‐c]thiazole 29 derivatives of imidazo[2,1‐b]thiazole were prepared. By nmr analysis of compound 29 , the existence of two stereoisomers resulting from both optical, due to centre of chirality at C7′a, and conformational isomerism, due to restricted C5? N6′ bond rotation were proved.     

(μ‐C‐meso‐5,5,7,12,12,14‐Hexa­methyl‐1,4,8,11‐tetra­aza­cyclo­tetra­decane‐N‐acetato‐1κ5N,N′,N′′,N′′′,O:2κO′)­tetra­chloro‐1κCl,2κ3Cl‐cobalt(III)­zinc(II)

The crystal structure of the title compound, [CoCl(C₁₈H₃₇N₄O₂){ZnCl₃}], has been determined by X‐ray diffraction.C‐meso‐5,5,7,12,12,14‐Hexa­methyl‐1,4,8,11‐tetra­aza­cyclotetradecane‐N‐acetate acts as a bridging ligand to coodinate with Co^III and Zn^II ions. The Co^III ion is six‐coordinate in a nearly octahedral environment provided by one Cl atom, four N atoms of the bridging ligand, and one O atom. The Zn^II ion is four‐coordinate in a distorted tetrahedral environment completed by three Cl atoms and an O atom of the bridging ligand.     

Synthesis of 3‐substituted pyrido[4′,3′:4,5]thieno[2,3‐d]pyrimidines and related fused thiazolo derivatives

Convenient syntheses of 3‐substituted ethyl 4‐oxo‐2‐thioxo‐1,2,3,4,5,6,7,8‐octahydropyrid[4′,3′:4,5]thieno[2,3‐d]pyrimidine‐7‐carboxylates 3a, b, 6, 11–13 , ethyl 3‐methyl‐5‐oxo‐2,3,6,9‐tetrahydro‐5 H‐pyrido[4′,3′:4,5]thieno[2,3‐d][1,3]thiazolo[3,2‐a]pyrimidine‐8‐7H‐carboxylate ( 4 ), and ethyl 2‐methyl‐5‐oxo‐2,3,6,9‐tetrahydro‐5H‐pyrido[4′,3′:4,5]thieno[2, 3‐d][1,3]thiazolo[3,2‐a]pyrimidine‐8[7H]carboxylate ( 8 ) from diethyl 2‐isothiocyanato‐4,5,6,7‐tetrahythieno[2,3‐c]pyridine‐3,6‐dicarboxylate ( 1 ) are reported. © 2003 Wiley Periodicals, Inc. Heteroatom Chem 14:201–207, 2003; Published online in Wiley InterScience (www.interscience.wiley.com). DOI 10.1002/hc.10131