By controlling the protonation level of the ligand (N,N′-bis(pyridin-3-ylmethyl)ethane-1,2-diamine, L), a series of metal–organic salts (MOSs) (1–2′) and coordination complexes (3–4′) were synthesized with metal halides MX₂ (M = Cu, Zn; X = Cl, Br, I). The structural diversities of 1–4′ revealed that the solvents, pH value and protonation levels of the ligand played significant roles in affecting the coordination conformations during the structural self-assembly process. The crystals of [4HL]⁴⁺·2[CuX₄]²⁻ (X = Cl 1, Br 1′) showed unusual reversible transformations by desorption/absorption of gaseous HCl–HBr and the progress of the solid–gas reaction was monitored by ex situ X-ray powder diffraction. Crystal [4HL]⁴⁺·2[ZnCl₄]²⁻ (2) transformed into [4HL]⁴⁺·2[ZnCl₄]²⁻·2H₂O (2′) due to the variation in concentration of [H⁺] in the mother solution. Crystal [Zn₂(2HL)I₆]·2CH₃OH (3) exhibited a phase transition upon exposing the powder to air for 24 hours, giving rise to a new phase [Zn₂(2HL)I₆]·2H₂O (3′).

中文翻译：

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含氮配体的逐步质子化对固态金属-有机盐和配位化合物形成的影响

通过控制配体的质子化水平（N，N'-双（吡啶-3-基甲基）乙烷-1，2-二胺，L），形成一系列金属-有机盐（MOSs）（1-2'）和用金属卤化物MX ₂（M = Cu，Zn; X = Cl，Br，I）合成配位配合物（3–4'）。1-4'的结构多样性表明，在结构自组装过程中，配体的溶剂，pH值和质子化水平在影响配位构象方面起着重要作用。[4HL] ⁴⁺ ·2 [CuX ₄ ] ²⁻（X = Cl 1，Br 1'）通过气态HCl-HBr的解吸吸收表现出异常的可逆转变，并且通过异位X射线粉末衍射监测了固-气反应的进程。由于[H ^+]浓度的变化，晶体[4HL] ⁴⁺ ·2 [ZnCl ₄ ] ^2-（2）转变为[4HL] ⁴⁺ ·2 [ZnCl ₄ ] ^2- ·2H ₂ O（2'）]在母液中。晶体[Zn ₂（2HL）I ₆ ]·2CH ₃ OH（3）在将粉末暴露于空气中24小时后表现出相变，从而产生新的相[Zn ₂（2HL）I ₆ ]·2H ₂ O（3'）。