Abstract
A new terthiophene-based imidazole luminophore 5,5’-(1H-thieno[3,4-d]imidazole-4,6-diyl)bis(thiophene-2-carboxylic acid) (TIBTCH2, 5) was synthesized in one step from previously reported 4,6-di(thiophen-2-yl)-1H-thieno[3,4-d]imidazole (DTTI, 4), and their photophysical properties were studied and compared accordingly. Under solvothermal conditions, reacting 5 with Mn(OAc)2 yielded a new three-dimensional metal-organic framework (MOF, 6) which was structurally defined by single-crystal X-ray diffraction. In 6, all Mn(II) ions octahedrally bind to carboxylate-O atoms to form a linear Mn3 secondary building unit (SBU) that contains three distinct coordination modes. Importantly, 6 exhibits dual functional properties of ligand-based emission and metal-based magnetic behaviors.
Highlights
Metal-organic frameworks (MOFs) are porous crystalline materials constructed with metal ions or clusters as secondary building units (SBUs) joined into infinite arrays by organic linkers
There is considerable current interest in the synthesis of emissive MOFs using customizable organic linkers and different metal SBUs driven by the goal of expanding the sensing applications of the MOF, as well as incorporating more diverse functional properties
MOFs with metalbased light emission can be utilized in molecular sensing by exploiting ligand-to-metal charge-transfer (LMCT) and by employing lanthanide (Ln(III)) metal centers coupled to organic “antennas”
Summary
Metal-organic frameworks (MOFs) are porous crystalline materials constructed with metal ions or clusters as secondary building units (SBUs) joined into infinite arrays by organic linkers. MOFs with metalbased light emission can be utilized in molecular sensing by exploiting ligand-to-metal charge-transfer (LMCT) and by employing lanthanide (Ln(III)) metal centers coupled to organic “antennas”. Ln(III)-based emissive MOFs harvest energy from the excited state of the organic linkers, which undergo internal resonant transfer to nearby Ln(III) centers, resulting in Ln-based emission. 22..33..PPhhoottoolulumminineesscceennttPPrrooppeerrttiieessooff TThheessoolliidd--ssttaatteepphhoottoolluummiinneesscceenncceepprrooppeerrttiieessooff55,, aass--ssyynntthheessiizzeedd 66,, aanndd aaccttiivvaatteedd 66 wweerree ssttuuddiieedd bbyy flfluuoorriimmeettrryy((FFiigguurree55).).TThhrereeemmaatetreirailaslshahvaevenenaeralyrlyidiednetnictaiclaplhpohtooptohpyhsiycsa-l ipcarol fiplreosfwileisthwointhe eoxnceitaetxicointabtiaonndbnaenadr 3n1e4anrm31, 4onnems,hoarnpe esmhaisrspioenmbiassnidonatb3a4n5dnamt,3a4n5dnomne, abnrdoaodneembirsosaiodnebmanisdsiaotn70b0annmd .aTt h70e0dantma .inTdhiceadteatthaaitntdhiecalutemtihnaetscthenecleuomf i6niesslciegnacned-obfa6seids. The nearly identical magnetic susceptibility behavior observed at low temperature in both the FC and ZFC measurements is most likely due to a phase transition from a paramagnetic (bulk disordered) phase to a more ordered phase.
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