Unprecedented Second‐Timescale Blue/Green Emissions and Iodine‐Uptake‐Induced Single‐Crystal‐to‐Single‐Crystal Transformation in Zn^II/Cd^II Metal–Organic Frameworks

Abstract

The long-persistent phosphorescent metal-organic framework (MOF) is a kind of highly desirable but rare material. Here, two new molecular MOF materials, {[Zn(tipa)Cl]⋅NO3⋅2 DMF}n (1) and {[Cd2(tipa)2Cl4]⋅6 DMF}n (2) (tipa = tri(4-imidazolylphenyl)amine), which have 3D twofold interpenetrated (utp) and 2D noninterpenetrated (kgd) topologies, respectively, are reported. They exhibit unexpected long-persistent emissions yet reported: At 77 K, they persist in glowing after stopping the UV irradiation on a timescale up to seconds at 77 K, which can be detected by the naked eye (ca. 2 s). Compounds 1 and 2 also undergo single-crystal-to-single-crystal (SC-SC) transformations through different routes; a simple anion-exchange route for 1 and a complicated replacement of μ1-Cl(-) ions by DMF molecules accompanying I3(-) captured in the void for 2.

Coordination Polymers with Intriguing Photoluminescence Behavior: The Promising Avenue for Greatest Long‐Lasting Phosphors

“…MOFs of related chemical formulae {[Zn(TIPA)Cl]NO 3 · 2DMF} n (12‐Zn) and {[Cd 2 (TIPA) 2 Cl 4 ] · 6DMF} n (13‐Cd, hereafter) [TIPA being tris(4‐imidazolylphenyl)amine] may be regarded as good examples of low‐temperature LLPs . Despite their related composition, they exhibit somewhat different open architectures (see structural details in Table ).…”

Face‐Capped M4L4 Tetrahedral Metal–Organic Cage: Iodine Capture and Release, Ion Exchange, and Electrical Conductivity

“…On the other hand, the increasing risk of radioactive iodine in the waste of the nuclear industry is dangerous to the health of humans, and this waste is very difficult to deal with because of iodine's long half‐life time of 15.7 million years . Recently, the capture of iodine and its derivatives by metal–organic cages (MOCs), metal–organic frameworks (MOFs) or porous coordination polymers (PCPs) has been vigorously investigated, showing fascinating prospects . For example, Zeng's group reported a highly stable MOF which exhibits kinetics of iodine loading and release similar to activated carbon .…”

“…Based on the rate constants derived from pseudo‐second‐order kinetics, specific interactions such as electrostatic interaction between I 3 − and MOC‐19 adsorbent may be expected for the rapid and high uptake of I 3 − anions. Therefore, we assume that the main uptake process of iodine species in aqueous solution of KI/I 2 should be dominated by I 3 − anions, which is reasonable since the coordination cages are positively charged, endowing stronger interaction with I 3 − anions than with neutral I 2 molecules …”

Fluorescent Cadmium Bipillared‐Layer Open Frameworks: Synthesis, Structures, Sensing of Nitro Compounds, and Capture of Volatile Iodine

“…[7][8][9][10][11][20][21][22][23][24][25][26][27][28][29][30][31][32] On the other hand, one aspect of current MOF studiesi sf ocused on trace elemente nrichment and adsorption, such as iodine( I 2 ). [33][34][35][36][37][38][39][40][41][42][43][44][45][46] Iodinei sag aseous fission productl iberated duringt he reprocessingo fs pent nuclear fuel, [42,47] and thusi s considered as am ajor waste of the nuclear industries. [37,48] Individuali sotopes of iodine are essentially radioactive and thus present unique exposure risks.…”