New star-shaped trinuclear Ru(II) polypyridine complexes of imidazo[4,5-f][1,10]phenanthroline derivatives: syntheses, characterization, photophysical and electrochemical properties

A series of new star-shaped trinuclear Ru(II) complexes of imidazo[4,5-f][1,10]phenanthroline derivatives, [{Ru(bpy)(2)}(3){μ-mes(1,4-phO-Izphen)(3)}](ClO(4))(6)·4H(2)O (6), [{Ru(phen)(2)}(3){μ-mes(1,4-phO-Izphen)(3)}](ClO(4))(6)·3H(2)O (7), [{Ru(bpy)(2)}(3){μ-mes(1,2-phO-Izphen)(3)}](ClO(4))(6)·4H(2)O (8), and [{Ru(phen)(2)}(3){μ-mes(1,2-phO-Izphen)(3)}](ClO(4))(6)·3H(2)O (9) [mes(1,4-phO-Izphen)(3) (4) = 2,4,6-tri methyl-1,3,5-tris(4-oxymethyl-1-yl(1H-imidazo-2-yl-[4,5-f][1,10]phenanthroline)phenyl)benzene and (mes(1,2-phO-Izphen)(3) (5) = 2,4,6-trimethyl-1,3,5-tris(2-oxymethyl-1-yl(1H-imidazo-2-yl[4,5-f][1,10]phenanthroline)phenyl)benzene] have been synthesized and characterized. Their photophysical and electrochemical properties have also been studied. The core molecule, 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene (1) and the trialdehyde intermediate, 2,4,6-trimethyl-1,3,5-tris(4-oxymethyl-1-formylphenyl)benzene (2) are characterized by single crystal X-ray diffraction: triclinic, P1[combining macron]. The complexes 6-9 exhibit Ru(II) metal centered emission at 618, 601, 615, and 605 nm, respectively, in fluid solution at room temperature. The emission profile and emission maxima are similar and independent of the excitation wavelength for each complex. The complexes 6-9 undergo metal centered oxidation and the E(1/2) values for the Ru(II)/Ru(III) redox couples are 1.33, 1.34, 1.35, and 1.35 V versus Ag/Ag(+), respectively, which are cathodically shifted with respect to that of the mononuclear complex [Ru(bpy)(2)(PIP)](2+) (PIP = 2-phenylimidazo[4,5-f][1,10]phenanthroline). The study demonstrates the versatility of the highly symmetric trinucleating imidazo[4,5-f][1,10]phenanthroline-based core ligands 4 and 5 in forming trinuclear Ru(II) complexes.     

Synthesis and characterisation of 3-armed dendritic molecules with triphenylbenzene or triphenyltriazine as core and triphenylene derivative as shells

Two series 3-armed dendritic molecules with their 1,3,5-tris(4-methyloxyphenyl) benzene or 2,4,6-tris(4- hydroxylphenyl)-1,3,5-s-triazine core and triphenylene derivative shells connected by soft hydrocarbon chains have been synthesised and fully characterised. Whether liquid crystal (LC) or photoluminescence materials have been tuned by changing the length of the soft chain and they have been studied by POM, DSC, XRD, UV-Vis and PL. The results show that all the new dendritic compounds display UV to blue fluorescence in solvents such as DCM, THF and acetone. The TC3 compound bearing 1,3,5-tris(4-hydroxylphenyl) benzene core exhibits LC property with rectangular columnar phase (Col_r) on cooling.     

含六苯基苯结构单元桨型分子的合成及光致发光特性

以1,3,5-三苯基苯为中心核, 4-乙烯基联苯为桥联结构, 通过Heck偶联反应合成了含六苯基苯结构单元的桨型分子, 对其结构进行了表征; 对桨型分子及其结构单元[包括4-乙烯基联苯、含六苯基苯结构的“臂”及其母体结构1,3,5-三(4-苯乙烯基苯基)苯]在溶液中的光致发光特性的研究结果表明, 桨型分子具有2个发光中心, 最大发射波长在蓝色光范围内分别为397和445 nm.     

1,3,5-三[(4’-乙炔基苯基)乙炔基]苯的合成

设计了多种合成路线制备芳香炔基树枝状化合物中间体1,3,5-三[(4’-乙炔基苯基)乙炔基]苯,通过一系列的合成路线和反应条件的对比,发现多官能团的端基炔化合物与芳基溴化合物之间发生多重Sonogashira反应时,常会生成不同取代程度的极性相似化合物,因而难以分离.采用多官能团的端基炔化合物与芳基碘化合物反应可以避免这种情况.最终确定以1,3,5-三溴苯和2-甲基-3-丁炔-2-醇为原料,制得中间产物1,3,5-三乙炔基苯;再以对碘苯胺和三甲基硅乙炔为原料,经重氮化化、卤代反应制得4-三甲基硅乙炔基碘苯;后者与1,3,5-三乙炔苯经Sonogashira反应、裂解去保护反应,制得化合物1,3,5-三[(4’-乙炔基苯基)乙炔基]苯.用1H NMR,13C NMR,元素分析等表征手段确认了中间体及最终产物的结构.     

Tandem one-pot intra- and inter-molecular McMurry coupling for the synthesis of bisindolostilbenophanes

Treatment of 3 equiv of indole-3-aldehyde with 1,3,5-trimethyl-2,4,6-tris(bromomethyl)benzene and 1,3,5-tris(bromomethyl)benzene gave the tris-alkylated products, which underwent both intra- and inter-molecular McMurry coupling in one-pot with low valent titanium to give indole-based stilbenophanes.     

Linear and star-shaped polynuclear Ru(II) complexes of 2-(2'-pyridyl)benzimidazolyl derivatives: syntheses, photophysical properties and red light-emitting devices

Two new star-shaped ligands with a 1,3,5-triphenylbenzene core, tmpb (1,3,5-tris[p-2-(2'-pyridyl)benzimidazolylphenyl]benzene), and a 2,4,6-tris(p-biphenyl)-1,3,5-triazine core, tmbt (2,4,6-tris[p-2-(2'-pyridyl)benzimidazolylbiphenyl]-1,3,5-triazine), have been synthesized. Their corresponding trinuclear Ru(II) complexes [Ru3(tmpb)(bpy)6](PF6)6 (3) and [Ru3(tmpt)(bpy)6](PF6)6 (4) have been obtained. Two dinuclear linear Ru(II) complexes with previously reported ligands bmb (1,4-bis[2-(2'-pyridyl)benzimidazolyl]benzene) and bmbp (4,4'-bis[2-(2'-pyridyl)benzimidazolyl]biphenyl) and formulae [Ru2(bmb)(bpy)4](PF6)4 (1) and [Ru2(bmbp)(bpy)4](PF6)4 (2) have also been synthesized. Photophysical and electrochemical properties of the new compounds have been investigated. All four compounds display a characteristic metal-to-ligand-charge transfer (MLCT) absorption band and emit a red light when excited at the maximum of the MLCT band with emission maximum at 624, 629, 623 and 625 nm, respectively in neat films at ambient temperature. The emission quantum efficiency of the four complexes in neat films was determined to be 0.15, 0.17, 0.04 and 0.05, respectively. Light emitting devices based on these four compounds were fabricated by spin-casting the compound as a neat film to an ITO substrate, followed by the deposition of an aluminium metal layer. All devices emit a deep red light and the device behavior resembles that of a light emitting electrochemical cell. The EL maximum of the devices 1, 2, 3, and 4 is at 637, 657, 678, and 655 nm, respectively. All four devices have a fast response time when a sufficiently high voltage is applied. The device based on 2 is the brightest with a maximum luminance of 133 cd m(-2) at 7 V. The performance of devices based on 1, 2, and 4 is in general much more efficient than the device based on [Ru(bpy)3](PF6)2, which was fabricated and evaluated under the same experimental conditions as for the devices based on 1-4.     

Stable gem-trifluoromethyl anionic σ-complexes based on 1,3,5-tris(sulfonyl)benzene derivatives and their transformations

A convenient synthetic procedures is described to obtain gem-trifluoromethyl anionic σ-complexes of 1,3,5-tris(fluorosulfonyl)benzene, 1,3,5-tris(β,β,β-trifluoroethoxysulfonyl)benzene, 1,3,5-tris(trifluoromethylsulfonyl)benzene as well as of 1,3,5-trinotrobenzene. Conditions for easy oxidation of these adducts into corresponding 2,4,6-tris(substituted)benzotrifluorides have been found. It is shown that the latter add trifluoromethyl anion to the 1 and 3 positions of the aromatic ring forming new anionic σ-complexes in different ratio. Structures and relative stabilities of the anionic adducts are discussed based on RI-MP2 quantum chemical calculations.     

Formation of two (6,3) networks showing structural diversity, Borromean topology and conformational chirality in the same crystal

Reaction of two tripodal ligands, 2,4,6-tris(4-((2-methyl-benzimidazol-1-yl)methyl)phenyl)-1,3,5-triazine (L1) and 1,3,5-tris(4-((2-methyl-benzimidazol-1-yl)methyl)phenyl)benzene (L2), with AgSbF6 led to formation of two types (6,3) networks in one single crystal, of which one is three-fold Borromean topologically entangled while the other is independent, showing the same chirality and sandwiched Borromean stacking.     

Structural criteria for the rational design of selective ligands. 3. Quantitative structure-stability relationship for iron(III) complexation by tris-catecholamide siderophores

We present an extended MM3 model for catecholamide ligands and their Fe(3+) complexes and the application of this model to understand how ligand architecture effects Fe(3+) binding affinity. Force field parameters were fit to geometries and energies from electronic structure calculations, and to crystal structure data. Optimized geometries are reported for phenol, acetamide, the phenol-phenol dimer, the acetamide-phenol dimer, and N-methylsalicylamide (HMSA) at the BLYP/DZVP2/A2 level of theory. Optimized geometries and relative energies are reported for the pseudo-octahedral ground state and the trigonal planar transition state of [Fe(CAT)(3)](3)(-) at the VWN/DZVP2/A1 level of theory. The MM3 model is validated by comparison of calculated structures with crystal structures containing 1,2-dihydroxybenzene (H(2)CAT) and 2,3-dihydroxy-N-methylbenzamide (H(2)MBA) fragments, crystal structures of [Fe(CAT)(3)](3)(-) and tris-catecholamide Fe(3+) complexes, and comparison of MM3 (6.8 kcal/mol) and VWN (5.9 kcal/mol) barriers for intramolecular octahedral inversion in [Fe(CAT)(3)](3)(-). The MM3 model also rationalizes the higher inversion barrier (14 to 18 kcal/mol) reported for [Ga(N,N-diisopropylterephthalamide)(3)](3)(-) ([Ga(DIPTA)(3)](3)(-)). Conformational searches were performed on enterobactin (H(6)ENT), 1,3,5-tris(2,3-dihydroxybenzamidomethyl)-2,4,6-triethylbenzene (H(6)EMECAM), 1,3,5-tris(2,3-dihydroxybenzamidomethyl)-2,4,6-trimethylbenzene (H(6)MMECAM), 1,3,5-tris(2,3-dihydroxybenzamidomethyl)benzene (H(6)MECAM), and 1,5,9-N,N',N' '-tris(2,3-dihydroxybenzoyl)cyclotriazatridecane (H(6)-3,3,4-CYCAM) and Fe(3+) complexes with each of these ligands. A conformational search also was done on the Fe(3+) complex with the 2,2',2' '-tris(2,3-dihydroxybenzamido)triethylammonium cation (H(7)TRENCAM(+)). The relationship between calculated steric energies and measured thermodynamic quantities is discussed, and linear correlations between formation constants and steric energy differences are reported. Extrapolation to zero strain predicts formation constants 8 +/- 5 orders of magnitude higher than that exhibited by ENT (10(49)) are possible. This prediction is supported by a formation constant of 10(63) estimated from the formation constant of [Fe(2,3-dihydroxy-N,N-dimethylbenzamide)(3)](3)(-) ([Fe(DMBA)(3)](3)(-)) by considering the entropic consequences of connecting three DMBA ligands to a rigid backbone. Structural criteria for the identification of improved tris-catecholate ligand architectures are presented.     

Modeling the mononuclear, dinuclear, and trinuclear copper(I) reaction centers of copper proteins using pyridylalkylamine ligands connected to 1,3,5-triethylbenzene spacer

The structure and O2-reactivity of copper(I) complexes supported by novel ligands, Pye2 (1,3,5-triethyl-2,4-bis((N-benzyl-N-(2-(pyridin-2-yl)ethyl)-)aminomethyl)benzene), Pye3 (1,3,5-triethyl-2,4,6-tris((N-benzyl-N-(2-(pyridin-2-yl)ethyl))aminomethyl)benzene), MePym2 (1,3,5-triethyl-2,4-bis((N-benzyl-N-(6-methylpyridin-2-ylmethyl))aminomethyl)benzene), and MePym3 (1,3,5-triethyl-2,4,6-tris((N-benzyl-N-(6-methylpyridin-2-ylmethyl))aminomethyl)benzene) have been examined. The ligands are designed to construct mono-, di-, and trinuclear copper(I) complexes by connecting two or three pyridylalkylamine metal-binding sites to a 1,3,5-triethylbenzene spacer. Thus, the reaction of the ligands with [CuI(CH3CN)4]X (X = PF6, CF3SO3) or CuICl gave the expected mononuclear copper(I) complexes [CuI(Pye2)(CF3SO3)] (1) and [CuI(Pye3)](CF3SO3) (2), dinuclear copper(I) complex [CuI2(MePym2)(Cl)]CuICl2 (3), and trinuclear copper(I) complex [CuI3(MePym3)(CH3CN)3](CF3SO3)3 (4), the structures of which were determined by X-ray crystallographic analysis. The mononuclear copper(I) complexes, 1 and 2, exhibit a distorted three-coordinate T-shape structure and a trigonal planar structure, respectively, which are very close to the coordination geometry of the CuA site of PHM (peptidylglycine alpha-hydroxylating monooxygenase) and the CuB site of CcO (cytochrome c oxidase). Notably, 1 and 2 showed a significantly high oxidation potential (990 mV vs SCE), thus showing virtually no reactivity toward O2. On the other hand, the metal centers of the dinuclear and trinuclear copper(I) complexes, 3 and 4, exhibit a distorted trigonal planar geometry and a trigonal pyramidal geometry, respectively. In contrast to the mononuclear copper(I) complexes, these dinuclear and trinuclear copper(I) complexes reacted with O2 to induce an aromatic ligand hydroxylation reaction involving an NIH-shift of one of the ethyl substituents on the benzene spacer. The NIH-shift of the alkyl substituent on the aromatic ring is strong evidence of the electrophilic aromatic substitution mechanism, although the active oxygen intermediate could not be directly detected during the course of the reaction. The biological relevance of the copper(I) complexes is also discussed on the basis of structure and O2-reactivity.     

Self-adaptation of manganese-chloride arrangement toward high spin Mn5(μ-Cl)4 cluster-based metal-organic framework with S = 15/2

The self-adaptation of manganese-chloride arrangement with the tripodal ligand 1,3,5-tris(benzimidazoyl-1-ylmethyl)-2,4,6-trimethylbenzene (Me(3)-TBzIm) afforded a rare 3D metal-organic framework, [Mn(5)Cl(10)(Me(3)-TBzIm)(4)](n) (1) showing a high spin ground state with S = 15/2.     

Palladium(II) complexes of bowls, pinwheels, cages, and N,C,N-pincers of starburst ligands 1,3,5-Tris(di-2-pyridylamino)benzene and 2,4,6-Tris(di-2-pyridylamino)-1,3,5-triazene

The reactions of Pd(II) ions with starburst ligands 1,3,5-tris(di-2-pyridylamino)benzene (tdab) and 2,4,6-tris(di-2-pyridylamino)-1,3,5-triazene (tdat) have been investigated. Complexes with the Pd:tdab (or tdat) ratio being 1:1 and 3:1 have been isolated and characterized. The structures of five new Pd(II) complexes containing the starburst ligands have been determined by X-ray diffraction analyses, which include chelate compounds [PdCl(2)(tdab)], 1, [(PdCl(2))(3)(tdab)], 2, [(Pd(OAc)(2))(3)(tdab)], 4, and [(Pd(OAc)(2))(3)(tdat)], 5, and a cyclometalated compound [Pd(OAc)(NCN-tdab)], 3. The Pd(II) ion in the 1:1 compound 1 is chelated by two pyridyl groups. Similarly, each Pd(II) center in the 3:1 compounds 2, 4, and 5 is chelated by two pyridyl groups. However, these three compounds display distinct structural features: 2 adopts a "bowl-shaped" structure, 4 has a "pinwheel"-like structure, and 5 has a "up-and-down" structure. Compounds 4 and 5 were examined in solution by variable-temperature (1)H NMR, which revealed that both compounds retain the "pinwheel" and the "up-and-down" structure, respectively. The observed structural preference by 4 and 5 is attributed to both electronic and steric factors.     

Synthesis and photophysical properties of hyperbranched polyfluorenes containing 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine as the core

A series of new hyperbranched polymers containing a 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core unit and polyfluorene chain arms have been synthesized via Suzuki coupling, and characterized by NMR, IR and GPC. All the polymers exhibit good thermal stability with a high decomposition temperature. By changing the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio the UV-vis absorption and emission spectra can be partially tuned. It has been found that the polymers containing a low ratio of 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine units (P1-P3) have an absorption maximum around 385 nm, localized in the polyfluorene chain, and a shoulder around 425 nm ascribable to a charge transfer state involving the fluorene and the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine core. Increasing the molar ratio of the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine unit enhances the charge transfer band which becomes dominant for P4. The LUMO level of these polymers is relatively low due to the electron affinity of the triazine group. The polymers show dual emission, with a structured band in the blue (410-440 nm), attributed to the polyfluorene, and a broad band in the red (470-500 nm) associated with the charge transfer state. All the polymers exhibit two-photon absorption activity in the range of 660 to 900 nm with the maximum two-photon absorption (TPA) cross-section red-shifted from the corresponding linear absorption. The values of the TPA cross-sections vary from 1000 to 5000 GM, following the 2,4,6-tris(thiophen-2-yl)-1,3,5-triazine/fluorene ratio.     

An efficient and facile one-pot synthesis of structurally unique 2,4,6-tris(arylchalcogeno)-1,3,5-triazine and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene

An efficient one-pot synthesis of a novel class of 2,4,6-tris(arylchalcogeno)-1,3,5-triazine (sulfur, selenium and tellurium) and 1,3,5-tris(arylchalcogeno)-2,4,6-trimethylbenzene (sulfur and selenium)-containing ligands has been developed based on the reaction of 2,4,6-trichloro-1,3,5-triazine and 1,3,5-tris(bromomethyl)-2,4,6-trimethylbenzene with the corresponding arylchalcogenide anions generated in aqueous tetrahydrofuran.     

Perfluoro-1,3,5-tris(p-oligophenyl)benzenes: Amorphous Electron-Transport Materials with High-Glass-Transition Temperature and High Electron Mobility

Perfluoro-1,3,5-tris(p-quaterphenyl)benzene (PF-13Y) and perfluoro-1,3,5-tris(p-quinquephenyl)benzene (PF-16Y) have been synthesized and characterized. They showed higher glass transition temperatures compared with perfluoro-1,3,5-tris(p-terphenyl)benzene (PF-10Y). Organic light-emitting diodes were fabricated using these materials as the electron-transport layers. PF-13Y and -16Y are better electron transporters than PF-10Y. The electron mobilities of PF-10Y and Alq₃ were measured by the time-of-flight technique. PF-10Y showed higher electron mobilities (10⁻⁴ cm²/V s) and weaker electric field dependence compared with Alq₃.     

Coordination copolymerization mediated by Zn4O(CO2R)6 metal clusters: a balancing act between statistics and geometry

Isolated successes of coordination copolymerization for the production of microporous coordination polymers (MCPs) have been reported recently; the logic for this synthetic approach has not been established nor have the key features of the synthetic conditions needed to generalize the method. Here, we establish guidelines for application of the copolymerization technique by exploring coordination modes and report, in addition to details on two previous coordination copolymers with exceptional properties, three new MCPs: UMCM-3 (Zn(4)O(2,5-thiophenedicaboxylate)(1.2)(1,3,5-tris(4-carboxyphenyl)benzene)(1.2)), UMCM-4 (Zn(4)O(1,4-benzenedicarboxylate)((3)/(2))(4,4',4'-tricarboxytriphenylamine)), and UMCM-5 (Zn(4)O(1,4-naphthalenedicarboxylate)(1,3,5-tris(4-carboxyphenyl)benzene)((4)/(3))). The MCPs prepared by the copolymerization technique demonstrate Brunauer-Emmett-Teller (BET) surface areas between 3500-5200 m(2)/g and high pore volumes (1.64-2.37 cm(3)/g). In addition, the alignment of poly(3-hexylthiophene) within mesoporous channels of UMCM-1 is reported as a demonstration of the unique properties of these hosts.     

具有三角架结构的丙二酸、β-二酮和吡唑衍生物的合成、结构及超分子自组装

本文系统的探讨了1,3,5-丙二酸衍生物取代基（2-5）,戊烷-2,4-二酮取代基(6),3,5-二甲基-1H-吡唑取代基-2,4,6-三乙基苯(7)的合成和结构。1H NMR分析表明,这些化合物在溶液中具有高度的对称性;X-单晶衍射分析确认这些化合物在固态均采取1,3,5-交替构象,即三个功能取代基团处在中心苯环平面的一边,而三个乙基则位于该中心苯环平面的另一边。分子内和分子间氢键是化合物4,5,7实现超分子自组装的主要作用力。化合物7（L）的吡唑取代基与铜离子（II）通过Cu-N的配位键作用形成笼状配合物8 (Cu3L2),在配合物8中,两配体分子7（L）采取了顺式面面相向的构象。     

Synthesis of novel indole based cyclophanes and cylindrical cyclophanes by tandem alkylation methodology using NaH

Treatment of 1 equiv of 1,3-bis(bromomethyl)benzene and 2,6-bis(bromomethyl)pyridine with 1 equiv of indole in the presence of NaH in THF afforded the symmetrical cyclophanes 1 and 2. Using similar methodology, cylindrical cyclophanes 3 and 4 were obtained from 2 equiv of 1,3,5-trimethyl-2,4,6-tris(bromomethyl)benzene and 1,3,5-tris(bromomethyl)benzene with 3 equiv of indole.     

Synthesis and self-association, absorption, and fluorescence properties of differentially functionalized hexakis(p-substituted-phenylethynyl)benzenes

The dual Sonogashira coupling reactions of 1,3,5-tribromo-2,4,6-triiodobenzene with p-X-phenylacetylene followed by another p-Y-phenylacetylene (X, Y = OSiMe(2)Bu-t or CO(2)Et) produced a series of differentially functionalized hexakis(p-substituted-phenylethynyl)benzenes with D(3)(h)() symmetry (3h: 1,3,5-X-2,4,6-Y) and C(2)(v)() symmetry (3g,i: 1,2,3,5-X-4,6-Y; 3f,j: 1-X-2,3,4,5,6-Y). In a similar manner, 1,3,5-tris(p-X-phenylethynyl)-2,4,6-tris(p-Y-phenylethynyl)benzenes and 1,2,3,5-tetrakis(p-X-phenylethynyl)-4,6-bis(p-Y-phenylethynyl)benzenes (3l: X = OSiMe(2)Bu-t, Y = NO(2); 3m,n: X = N(n-octyl)(2), Y = NO(2); 3o,p: X = N(n-octyl)(2), Y = CH(OCH(2)CH(2)O); 3q,r: X = N(n-octyl)(2), Y = CHO; 3s,t: X = N(n-octyl)(2), Y = CH=C(CN)(2)) were prepared. Compounds 3 with electron-withdrawing groups self-aggregated by a pi-pi stacking interaction and solvophobic effect. In the absorption and fluorescence spectra of 3, lambda(max)(abs) and lambda(max)(em) showed red shifts as the donor-acceptor dipole at the end functional groups of the para position was increased. In the absorption spectra, lambda(max)(abs) showed red shifts upon increasing the number of combination of electron-donating and -withdrawing groups on the diagonal line in a molecule, whereas lambda(max)(em) in the fluorescence spectra exhibited red shifts upon decreasing the molecular symmetry.     

Cation selectivity of ionophores based on tripodal thiazole derivatives on benzene scaffold

The synthesis and potentiometric evaluation of new 1,3,5-tris(thiazolylcarbethoxy)-2,4,6-trimethylbenzene (3), 1,3,5-tris(thiazolylhydroxy)-2,4,6-trimethylbenzene (4), 1,3,5-tris(thiazolylmethyl)-2,4,6-trimethylbenzene (5), and 1,3,5-tris(thiazolylphenyl)-2,4,6-trimethylbenzene (6), toward mono and divalent cations under various pH conditions are outlined. The ion-selective properties of the newly synthesized compounds were studied by measuring the potentiometric responses of the 3-, 4-, 5-, and 6-based membrane electrodes to alkali metal, alkaline earth metal, ammonium, and transition metal ions, under various pH conditions. The 3-based electrode exhibited a Nernstian response to ammonium and potassium under alkaline pH conditions, while the other three electrodes showed a poor potentiometric performance. All electrodes showed substantial responses to silver ion under acidic condition, but there was almost nil response to other transition metal ions (Fe²⁺, Co²⁺, Zn²⁺, Ni²⁺, Pb²⁺, Cd²⁺, Cu²⁺ and Hg²⁺). The 3- and 5-based electrodes resulted in near Nernstian responses (51.3 mV and 59.5 mV/pAg⁺, respectively) with low detection limits (100 ppt), while the 4- and 6-based ones showed sub-Nernstian below 40 mV/pAg⁺. The results were interpreted with semi-empirically modeled structures.