A Cu‐Based Near‐IR Active MOF with an Ion‐Pair Guest Exhibiting Versatile and Selective Gas‐Solid Reactivity
Year: 2025
Type: article
Abstract: Metal–organic frameworks (MOFs) that react spontaneously and selectively with gases or vapors are useful in separation and purification processes, but are very scarce since only a few MOFs are capable of undergoing structural transformations. Simultaneous incorporation of cations and anions in a MOF is, as far as is known, never been observed. Here a new MOF: (Me 2 NH 2 )(Cu I Cl 2 )@[Cu II 4 (INA) 4 Cl 2 O]·1.5dmf ( 3 ) (INA = isonicotinate, dmf = N,N’‐dimethylformamide) is presented that simultaneously incorporates Me 2 NH 2 + cations and CuCl 2 − anions. Furthermore, to the best of our knowledge, MOF 3 is the first transition metal‐based near‐IR active MOF. A systematic reactivity study with highly reactive gases and vapors shows that, in the presence of NH 3 , MOF 3 presents a single‐crystal‐to single crystal transformation into [Cu(INA)(OH)]·H 2 O ( 4 ‐ NH 3 ), a 3D MOF containing unprecedented [Cu(µ 3 ‐OH)] n n– chains. With HCl or HCOOH vapors, MOF 3 shows a dissolution‐recrystallization structural transformation into (HINA) 2 [Cu 2 Cl 6 (H 2 O) 2 ] ( 5 ‐ HCl ) or the 3D MOF (Me 2 NH 2 )[Cu(HCOO) 3 ] ( 6 ‐ For ). In contrast, MOF 3 remains stable under vapors of H 2 SO 4 , H 3 PO 4 , Et 3 N, acetone, acetonitrile, methanol, ethanol, and pyridine. Theoretical calculations confirm the spontaneous nature of these transformations. Density functional theory (DFT) calculations show that the reduction of Cu II to Cu I in the host helps to explain such exceptional optical properties.
Source: Advanced Materials
Language: English
Subfield: Inorganic Chemistry
Field: Chemistry
Domain: Physical Sciences
Open Access status: hybrid
Estimated APC paid: $6,070
Funders: European Commission, Generalitat de Catalunya, Generalitat Valenciana, Institució Catalana de Recerca i Estudis Avançats, Ministerio de Ciencia e Innovación, California State University, Chico, Departament d'Universitats, Recerca i Societat de la Informació, European Regional Development Fund, Agencia Estatal de Investigación, Conselleria de Cultura, Educación y Ciencia, Generalitat Valenciana, Conselleria de Innovación, Universidades, Ciencia y Sociedad Digital, Generalitat Valenciana
Awards: G1000029615, G1047231290, G1076211860, G1119952352, G115428345, G1168373365, G1204740081, G120905174, G123897006, G1272927172, G1293425506, G1300799387, G145641598, G1510469474, G1530851820, G1622782223, G1843157804, G1969072752, G2042725634, G2089336561, G2513399825, G2543706835, G2586187451, G2974855460, G2988934680, G3193775030, G3274226867, G3480869486, G348919436, G357246561, G3648286471, G418733018, G4444876874, G4445310383, G4504427362, G4526231891, G482457837, G5080475149, G531036588, G542410139, G5922099756, G5959719260, G6033532046, G612887951, G7084143925, G7434936867, G8373511800, G8395048066, G849817630, G8938532399
OpenAlex ID: W4415620118