The multistep synthesis of a versatile new 4-substituted 3,5-bis(2-pyridyl)-1,2,4-triazole (Rdpt) ligand, 4-[4-(2-aminomethyl)phenyl]-3,5-bis(2-pyridyl)-4 H-1,2,4-triazole (apdpt), is reported, which features a reactive aminomethyl para-substituent on the phenyl group that points "out of the back" of the triazole. This enables further functionalisation under mild conditions by using a range of esters to form an amide link. Specifically, this proof of principle study demonstrates the synthesis of apdpt successfully appended with gold-binding thioctic acid (tpdpt), graphene-binding/emissive pyrene/propylpyrene (prdpt/pbdpt), and a Langmuir-Blodgett film-forming polyethylene glycol (PEG) tail (pgdpt). These ligands are subsequently reacted with [Fe(pyridine)4 (NCBH3 )2 ] to give the mononuclear iron(II) complexes [Fe(Rdpt)2 (NCBH3 )2 ]⋅solvent, in which Rdpt/solvent is tpdpt/2.5 H2 O (1), prdpt/0.5 CHCl3 ⋅H2 O (2), and pbdpt/0.5 CHCl3 ⋅2 H2 O  (3), as red powders. Magnetic studies on these powders indicate that the complexes undergo only very gradual and incomplete spin crossover, from completely or mostly high spin at 300 K, to half or three-quarters high spin at 50 K. Gold nanoparticles are successfully functionalised with the thioctic acid tpdpt ligand to give tpdpt@Au with an average diameter (as determined by TEM) of (3.1±0.7) nm. Preliminary studies on the two pyrene systems in dimethylformamide show that upon excitation at λ=345 nm the blue fluorescence observed for the free ligands is retained, essentially unaffected, in the respective complexes.

中文翻译：

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迈向双功能自旋交叉复合物。

通用的新型4-取代的3,5-双（2-吡啶基）-1,2,4-三唑（Rdpt）配体，4- [4-（2-氨基甲基）苯基] -3,5-的多步合成据报道双（2-吡啶基）-4 H-1,2,4-三唑（apdpt），其特征在于在苯基上的反应性氨基甲基对位取代基指向三唑的“背面”。通过使用一系列酯形成酰胺键，可以在温和条件下进一步官能化。具体来说，这项原理研究证明成功地合成了apdpt，并成功地结合了金结合的硫辛酸（tpdpt），石墨烯结合/发射pyr /丙基py（prdpt / pbdpt）和Langmuir-Blodgett成膜聚乙二醇（PEG ）尾巴（pgdpt）。这些配体随后与[Fe（吡啶）4（NCBH3）2]反应，得到单核铁（II）配合物[Fe（Rdpt）2（NCBH3）2]·溶剂，其中Rdpt /溶剂为tpdpt / 2.5 H2 O（1），prdpt / 0.5 CHCl3⋅H2O（2）和pbdpt / 0.5 CHCl3⋅2H2 O（3），为红色粉末。对这些粉末的磁性研究表明，复合物仅经历了非常缓慢和不完全的自旋交叉，从300 K的完全或大部分为高自旋，到50 K的高度自旋为四分之三或四分之三。配体得到tpdpt @ Au，其平均直径（由TEM测定）为（3.1±0.7）nm。对二甲基甲酰胺中两个pyr系统的初步研究表明，在λ= 345 nm处激发后，观察到的游离配体蓝色荧光得以保留，基本上不受影响，