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Materials 2021, 14, 1786 2 of 19 Materials 2021, 14, 1786 Lanthanide-based coordination polymer (LnCP) luminescence, among other proper- boxylates [6–11], or introducing co-ligands, such as phenanthroline, bipyridine, 1,2-bis(4- pyridyl)ethylene and others [12–18]. These strategies are extremely important when the ties, can be improved or changed: using selected organic ligands, such as aromatic car- LnCP is prepared using aqueous solutions, since they tend to promote the replacement of the LnCP is prepared using aqueous solutions, since they tend to promote the replacement water molecules present in the CP structure by the ligands [19,20], decreasing the effect of of water molecules present in the CP structure by the ligands [19,20], decreasing the effect luminescence quenching associated to the presence of such molecules [3,21,22]. Several of luminescence quenching associated to the presence of such molecules [3,21,22]. Sev- CPs based on isophthalic derivatives and Ln ions have been reported recently with differ- 2 of 20 eral CPs based on isophthalic derivatives and Ln ions have been reported recently with 3+ 3+ 2+ 2+2− 2− ent applications, namely detection of Fe [15,23], Cu , CrO7 , nitrobenzene [24], 2,4-dini- different applications, namely detection of Fe [15,23], Cu , CrO7 , nitrobenzene [24], trophenol [23], antibiotics [25], alkylamines [26], as well as adsorption and removal of F− 2,4-dinitrophenol [23], antibiotics [25], alkylamines [26], as well as adsorption and re- − from water [27]. Some of those studies focus on strategies to improve the PL properties. moval of F from water [27]. Some of those studies focus on strategies to improve the The work reported by Yan et al. revealed that an isophthalic acid-based metal-organic PL properties. The work reported by Yan et al. revealed that an isophthalic acid-based 3+ 3+ 3+ 3+ mfreatmale-owrgoarkni(cMfrOamF)ewaosrkab(MleOtoF)sewnassitaizbelethtoesleunmsitnizesectehnecleuomfiSnmesceanncdeoDfySmmaatenrdiaDlsyde- mspaitteritahlespdrespeintecethoef sperveesreanlcweaotfersemvoelreacluwleasteinr tmheolsetcrucletusrien[t2h8e].sAtrnuocthuerrer[e2c8u].rrAentostthreart- 3+ 3+ 3+ 3+ regcuyrrisentthsetruastegoyfidsothpeinugseaogfednotsp,isnugcahgeanstEs,usucohraTsbEu, tooirnTcbreas,etotihnecreemasiesstihoeneimntiessnisointy inretleantseidtytoremlaetteadl-tcoenmteerteadl-ceemnitsesrieodnsem[29is–s3io2]n.sK[y2p9–ri3a2n]i.dKouypertialn.i[d3o3u] deetsaclr.ib[3e3t]hdatestchreibre- tphalatctehmeerneptloafcseomlveennttomfsollevceunletsmboyletceurmleisnbayllytecromoirndailnlaytcinogorodrignantincgmorlgeacunilcesmwoiltehcumleusl- wtiipthlemfunlctitpiolenaful gnrcotiuopnsa,lignrcoludpisn,gin–cOluHd,i–nSgH–,O–HN,H––SHan,d–N–NHH–2a,ncadn–iNncHrea,sceanupintcore1a6s-teimupes 2 ttoh1e6v-tailmuesotfheemviassluioenoqfueamnitsusmionyiqeulda.nTtuhmeaynitelndn.aTehfefeacnttwenansaobesffeercvtewdainsoabTsbe-rbvaesdedinCaP Twb-itbhas5e-(d1HC-Ppwyriathzo5l-3(1-yHl)-ipsyorpahztohla-3li-cyal)ciisdopashathlaigliacnadc,idanads tahilsigCaPndre, vaenadletdhihsiCghP srelveectailveidty 3− haingdh selnescitivityaindthsendseiteivctiitoyninofthPeOd4etienctaioqnueoofuPsOsolutinonaq[3u4e]o.us solution [34]. 3− 4 The multiple examples of CPs prepared using isophthalic acid derivatives and their The multiple examples of CPs prepared using isophthalic acid derivatives and their versatile application, combined with our recent research interests in the design and de- versatile application, combined with our recent research interests in the design and devel- velopment of multifunctional crystalline materials [35–43], justify our motivation in the opment of multifunctional crystalline materials [35–43], justify our motivation in the prep- preparation of a series of LnCPs. Herein, four LnCPs, based on 5-aminoisophthalic acid aration of a series of LnCPs. Herein, four LnCPs, based on 5-aminoisophthalic acid − (H aip − , Scheme 1), prepared by hydrothermal (HT) or microwave-assisted synthesis (H22aip , Scheme 1), prepared by hydrothermal (HT) or microwave-assisted synthesis (MWAS) methods, are reported. Considering that the PL properties of these materials (MWAS) methods, are reported. Considering that the PL properties of these materials are are highly dependent on several factors, including the existence of water molecules in highly dependent on several factors, including the existence of water molecules in the the crystal structure, our main objectives are the preparation of CP using a green chem- crystal structure, our main objectives are the preparation of CP using a green chemistry istry approach, as well as the evaluation the influence of water content and structural approach, as well as the evaluation the influence of water content and structural differ- differences in the PL properties of these materials. The PL properties of the LnCPs were ences in the PL properties of these materials. The PL properties of the LnCPs were studied studied in the solid state, at room temperature, including the determination of fluores- in the solid state, at room temperature, including the determination of fluorescence inten- cence intensity, PL excitation and lifetime, using the powders and a PMMA—poly(methyl sity, PL excitation and lifetime, using the powders and a PMMA—poly(methyl methacry- methacrylate—encapsulation method. late—encapsulation method. Scheme 1. Chemical structure of the ligands used in the preparation of the CPs: (a) 5-ami- Scheme 1. Chemical structure of the ligands used in the preparation of the CPs: (a) 5- noisophthalic acid (H2aip) and (b) phenathroline (phen). aminoisophthalic acid (H2aip) and (b) phenathroline (phen). 22. .MaatteerriiaallssaandMeetthhooddss 2.1. Materials 2.1. Materials Reagents and solvents used in the preparation of CP were purchased as reagent-grade Reagents and solvents used in the preparation of CP were purchased as reagent- and used without further purification, unless otherwise stated. MWAS was carried out in a grade and used without further purification, unless otherwise stated. MWAS was carried circular single-mode cavity instrument (300 W max magnetron power output) from CEM out in a circular single-mode cavity instrument (300 W max magnetron power output) (CEM Microwave Technology Ltd., Buckingham, UK). from CEM (CEM Microwave Technology Ltd., Buckingham, UK). For the PL characterization, spectrochemical grade solvents were used for optical For the PL characterization, spectrochemical grade solvents were used for optical measurements. Poly(methyl methacrylate) (PMMA) was obtained from Sigma-Aldrich measurements. Poly(methyl methacrylate) (PMMA) was obtained from Sigma-Aldrich (Darmstadt, Germany) and toluene was purchased from Merck Millipore (Darmstadt, Germany) without further purification.PDF Image | Green Chemistry with Supercritical CO2 and Enzymes
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