Single‐Layered Hybrid Materials Based on 1D Associated Metalorganic Nanoribbons for Controlled Release of Pheromones

Abstract

An ew family of stable layered organic-inorganic materials has been prepared, in one-step solvothermal process. They are based on an ordered nickel cluster-type nanoribbons separated from each other by specific alkyl (heptyl-or dodecyl-)a rylic mono-carboxylate moieties acting as molecular spacers,p erpendicular to the 1D inorganic chains.T hese organic spacers contain hydrocarbon tails with different length which control the separation level between inorganic 1D subunits,i nhibiting the 3D growth of conventional DUT-8-type metal-organic frameworks (MOFs). The lamellar nature of the materials formed was studied and confirmed by different characterization techniques,showing the structural location of individual organic and inorganic building units.T hey have been successfully used as al ong-lasting biodegradable and water-proof materials for controlled release of chemicals,such as pheromones for sustainable treatment of insect plagues.Nanometric sheets are fundamental structural units to obtain novel families of versatile lamellar materials,t heir preparation, study,and applicability being atrue challenge in materials science.T hey are useful since it is possible to take advantage of their capacity to be modified and used as integral parts of new hybrid nanocomposite solids.I norganic sheets,based on metallic oxides,are essential structural units which are provide different types of lamellar solids with several long-order topologies,s patial arrangement, and physico-chemical characteristics. [1][2][3] These layered materials can be modified by the spatial alteration of the individual layers through swelling,intercalation, or exfoliation processes to obtain more accessible solids, [4][5][6] and it is possible to incorporate additional functions during post-synthesis treat-ments. [7][8][9] In the case of metalorganic structures,s uch as metal-organic frameworks (MOFs), the formation of modifiable layered precursors is not frequent, and usually 3D structures based on the coordination binding between metallic nodes and rigid bi-carboxylate linkers are obtained. [10,11] Preparation of modifiable layered metalorganic precursors formed by individual organic-inorganic layers obtained by direct synthesis,isamatter of interest, and has been studied in 2D coordination polymers. [12,13] Incipient studies related with the formation of MOF nanosheets by modulation of growth kinetics have also been reported. [14] Nevertheless,t he existence of 3D conventional MOFs which exhibited lamellar structural tendencyi nt he spatial distribution of their structural building units,could be indicative of the possibility to obtain lamellar metalorganic structures. [15][16][17][18][19][20][21] Taking the above into account, we have succeeded herein in the preparation of different layered organic-inorganic materials,i nao ne-step process.T he materials are based on ordered associated nickel-cluster-type nanoribbons,similar to sub-networks detectable in 3D DUT-8 materials,separated by specific alkyl arylic mono-carboxylate moieties acting as mo...