0628bb5857db1221a59790a981d289b2 molecules_a2022v27n4p1365.pdf eaa53f72460a565b144093b8b611f589d9f3e334 molecules_a2022v27n4p1365.pdf b331a519a9d5b6f05c3972d5a02e41008c4470dfa9ab2e7abe32d6ccc08c7b37 molecules_a2022v27n4p1365.pdf Title: Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid Subject: Aggregation between discrete molecules is an essential factor to prevent aggregation-caused quenching (ACQ). Indeed, functional groups capable of generating strong hydrogen bonds are likely to assemble and cause ACQ and photoinduced electron transfer processes. Thus, it is possible to compare absorption and emission properties by incorporating two ligands with a different bias toward intra- and intermolecular interactions that can induce a specific structural arrangement. In parallel, the electron-donor or electron-withdrawing character of the functional groups could modify the Highest Ocuppied Molecular Orbital (HOMO)–Lowest Unocuppied Molecular Orbital (LUMO) energy gap. Reactions of M(OAc)22H2O (M = Zn(II) and Cd(II); OAc = acetate) with 1,3-benzodioxole-5-carboxylic acid (Piperonylic acid, HPip) and 4-acetylpyridine (4-Acpy) or isonicotinamide (Isn) resulted in the formation of four complexes. The elucidation of their crystal structure showed the formation of one paddle-wheel [Zn(-Pip)2(4-Acpy)]2 (1); a mixture of one dimer and two monomers [Zn(-Pip)(Pip)(Isn)2]22[Zn(Pip)2(HPip)(Isn)]2MeOH (2); and two dimers [Cd(-Pip)(Pip)(4-Acpy)2]2 (3) and [Cd(-Pip)(Pip)(Isn)2]2MeOH (4). They exhibit bridged (1, 2-1:1), bridged, chelated and monodentated (2, 2-1:1, 1-1:1 and 1-1), or simultaneously bridged and chelated (3 and 4, 2-2:1) coordination modes. Zn(II) centers accommodate coordination numbers 5 and 6, whereas Cd(II) presents coordination number 7. We have related their photophysical properties and fluorescence quantum yields with their geometric variations and interactions supported by TD-DFT calculations. Keywords: Zn(II) and Cd(II); 4-acetylpyridine; isonicotinamide; piperonylic acid; photoluminescence Author: Francisco Sánchez-Férez, Joaquim Mª Rius-Bartra, José A. Ayllón, Teresa Calvet, Mercè Font-Bardia and Josefina Pons Creator: LaTeX with hyperref Producer: pdfTeX-1.40.21 CreationDate: Thu Feb 24 06:34:20 2022 CET ModDate: Thu Feb 24 06:54:00 2022 CET Tagged: no UserProperties: no Suspects: no Form: none JavaScript: no Pages: 29 Encrypted: no Page size: 595.276 x 841.89 pts (A4) Page rot: 0 File size: 7088322 bytes Optimized: no PDF version: 1.7 name type encoding emb sub uni object ID ------------------------------------ ----------------- ---------------- --- --- --- --------- LSPCRN+EURM10 Type 1 Builtin yes yes no 10 0 TUZDPU+URWPalladioL-Bold Type 1 Custom yes yes no 14 0 KPFZXI+URWPalladioL-Roma Type 1 Custom yes yes no 19 0 MDGFII+URWPalladioL-Ital Type 1 Custom yes yes no 23 0 PBNQNR+URWPalladioL-BoldItal Type 1 Custom yes yes no 27 0 ZYAKOB+CMSY10 Type 1 Builtin yes yes no 31 0 HKBJPQ+VnURWPalladioL Type 1 Custom yes yes no 35 0 DNLDOC+VnURWPalladioL-Bold Type 1 Custom yes yes no 40 0 MCBCCI+SourceSansRoman-Regular Type 1C Custom yes 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edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@46daef40 Item: Title: Crystal and Extended Structure of Zn(II) Complexes Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@12f41634 Item: Title: Crystal and Extended Structure of Cd(II) Compounds Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@13c27452 Item: Title: Structure and Geometric Evaluation Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@262b2c86 Item: Title: Photophysical Properties Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@371a67ec Item: Title: Electronic Calculations Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@5ed828d Item: Title: Conclusions Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@50d0686 Item: Title: Experimental Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@7a3d45bd Children: Item: Title: Materials and General Details Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@1e7c7811 Item: Title: Synthesis of Complexes 1 4 Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@77ec78b9 Item: Title: X-ray Crystallography Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@1a3869f4 Item: Title: References Destination: edu.harvard.hul.ois.jhove.module.pdf.PdfSimpleObject@a38d7a3 Info: Title: Tuning Photophysical Properties by p-Functional Groups in Zn(II) and Cd(II) Complexes with Piperonylic Acid Author: Francisco Sánchez-Férez, Joaquim Mª Rius-Bartra, José A. Ayllón, Teresa Calvet, Mercè Font-Bardia and Josefina Pons Subject: Aggregation between discrete molecules is an essential factor to prevent aggregation-caused quenching (ACQ). Indeed, functional groups capable of generating strong hydrogen bonds are likely to assemble and cause ACQ and photoinduced electron transfer processes. Thus, it is possible to compare absorption and emission properties by incorporating two ligands with a different bias toward intra- and intermolecular interactions that can induce a specific structural arrangement. In parallel, the electron-donor or electron-withdrawing character of the functional groups could modify the Highest Ocuppied Molecular Orbital (HOMO) Lowest Unocuppied Molecular Orbital (LUMO) energy gap. Reactions of M(OAc)22H2O (M = Zn(II) and Cd(II); OAc = acetate) with 1,3-benzodioxole-5-carboxylic acid (Piperonylic acid, HPip) and 4-acetylpyridine (4-Acpy) or isonicotinamide (Isn) resulted in the formation of four complexes. The elucidation of their crystal structure showed the formation of one paddle-wheel [Zn(-Pip)2(4-Acpy)]2 (1); a mixture of one dimer and two monomers [Zn(-Pip)(Pip)(Isn)2]22[Zn(Pip)2(HPip)(Isn)]2MeOH (2); and two dimers [Cd(-Pip)(Pip)(4-Acpy)2]2 (3) and [Cd(-Pip)(Pip)(Isn)2]2MeOH (4). They exhibit bridged (1, 2-1:1), bridged, chelated and monodentated (2, 2-1:1, 1-1:1 and 1-1), or simultaneously bridged and chelated (3 and 4, 2-2:1) coordination modes. Zn(II) centers accommodate coordination numbers 5 and 6, whereas Cd(II) presents coordination number 7. We have related their photophysical properties and fluorescence quantum yields with their geometric variations and interactions supported by TD-DFT calculations. Keywords: Zn(II) and Cd(II); 4-acetylpyridine; isonicotinamide; piperonylic acid; photoluminescence Creator: LaTeX with hyperref Producer: pdfTeX-1.40.21 CreationDate: Thu Feb 24 06:34:20 CET 2022 ModDate: Thu Feb 24 06:54:00 CET 2022 ID: 0x8896f2cc9d3e65fc1e4e306604cced48, 0x8896f2cc9d3e65fc1e4e306604cced48 Filters: FilterPipeline: FlateDecode Fonts: Type1: Font: BaseFont: PDXFNG+PazoMath-Bold FontSubset: true FirstChar: 68 LastChar: 68 FontDescriptor: FontName: PDXFNG+PazoMath-Bold Flags: Symbolic FontBBox: -10, -266, 829, 695 FontFile: true Font: BaseFont: HKBJPQ+VnURWPalladioL FontSubset: true FirstChar: 129 LastChar: 226 FontDescriptor: FontName: HKBJPQ+VnURWPalladioL Flags: Symbolic FontBBox: -166, -283, 1021, 943 FontFile: true EncodingDictionary: Differences: true Font: BaseFont: VQEPBT+PazoMath-Italic FontSubset: true FirstChar: 97 LastChar: 113 FontDescriptor: FontName: VQEPBT+PazoMath-Italic Flags: Symbolic FontBBox: -70, -277, 902, 733 FontFile: true Font: BaseFont: 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