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Its basicity properties and complexation features toward Cu<jats:sup>II<\/jats:sup>, Zn<jats:sup>II<\/jats:sup>, Cd<jats:sup>II<\/jats:sup> and Pb<jats:sup>II<\/jats:sup> have been studied in aqueous solutions by means of potentiometric, UV\/Vis spectroscopy and fluorescence emission measurements and compared with those of ligand L2, in which a 1,10\u2010phenanthroline moiety replaces the dipyridine unit of L1. In metal coordination, L1 shows a marked selectivity toward Cd<jats:sup>II<\/jats:sup> over Zn<jats:sup>II<\/jats:sup> and Pb<jats:sup>II<\/jats:sup>. The crystal structures of its metal complexes shows that L1 possesses a preferential tetradentate binding site for metal cations, composed of the dipyridine unit and the two adjacent benzylic amine groups. This binding site has the proper dimension and conformation to selectively coordinate the Cd<jats:sup>II<\/jats:sup> ion, as confirmed by DFT calculations carried out on the complexes. This coordinative zone is lost in L2. The rigidity of phenanthroline does not allow the simultaneous binding of both the benzylic amine groups to Zn<jats:sup>II<\/jats:sup> and Cd<jats:sup>II<\/jats:sup> and, in fact, one benzylic amine is not coordinated to these metal cations. The fluorescence emission properties of the L1 and L2 complexes are strongly pH dependent. Only the Zn<jats:sup>II<\/jats:sup> and Cd<jats:sup>II<\/jats:sup> complexes with L1 display fluorescence emission at neutral pH. This feature is related to the formation in solution at pH\u20057 of emissive protonated complexes of the type [M(H<jats:sub><jats:italic>x<\/jats:italic><\/jats:sub>L)]<jats:sup>(2+<jats:italic>x<\/jats:italic>)+<\/jats:sup> (<jats:italic>x<\/jats:italic>=1\u20133), in which all the nitrogen donors are involved in metal or proton binding. The emissive characteristics of these protonated complexes are confirmed by the fluorescence emission spectra collected on the [Zn(HL1)Br][ClO<jats:sub>4<\/jats:sub>]<jats:sub>2<\/jats:sub> and [Cd(HL1)Br][ClO<jats:sub>4<\/jats:sub>]<jats:sub>2<\/jats:sub> solid compounds dissolved in CH<jats:sub>3<\/jats:sub>CN. Conversely, the Zn<jats:sup>II<\/jats:sup> and Cd<jats:sup>II<\/jats:sup> complexes with L2 are not emissive; in fact, they contain a benzylic amine group not involved in metal or proton binding that can quench the fluorescence emission of the fluorophore, thanks to a photoinduced electron\u2010transfer process.<\/jats:p>","DOI":"10.1002\/chem.200900283","type":"journal-article","created":{"date-parts":[[2009,6,5]],"date-time":"2009-06-05T15:02:10Z","timestamp":1244214130000},"page":"8049-8063","source":"Crossref","is-referenced-by-count":30,"title":["Polyamine Receptors Containing Dipyridine or Phenanthroline Units: Clues for the Design of Fluorescent Chemosensors for Metal Ions"],"prefix":"10.1002","volume":"15","author":[{"given":"Carla","family":"Bazzicalupi","sequence":"first","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Andrea","family":"Bencini","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Silvia","family":"Biagini","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Antonio","family":"Bianchi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Enrico","family":"Faggi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Claudia","family":"Giorgi","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Melania","family":"Marchetta","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Federico","family":"Totti","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]},{"given":"Barbara","family":"Valtancoli","sequence":"additional","affiliation":[],"role":[{"vocabulary":"crossref","role":"author"}]}],"member":"311","published-online":{"date-parts":[[2009,8,4]]},"reference":[{"key":"e_1_2_6_1_2","unstructured":"Selected reviews:"},{"key":"e_1_2_6_2_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2007.11.009"},{"key":"e_1_2_6_3_2","first-page":"1","volume-title":"Topics in Fluorescence Spectroscopy, Vol.\u20059","author":"Prodi L.","year":"2005"},{"key":"e_1_2_6_4_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)00239-3"},{"key":"e_1_2_6_5_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(00)00246-0"},{"key":"e_1_2_6_6_2","doi-asserted-by":"publisher","DOI":"10.1016\/j.ccr.2006.01.006"},{"key":"e_1_2_6_7_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr010421e"},{"key":"e_1_2_6_8_2","volume-title":"Molecular Fluorescence","author":"Valeur B.","year":"2002"},{"key":"e_1_2_6_9_2","doi-asserted-by":"publisher","DOI":"10.1021\/cr960386p"},{"key":"e_1_2_6_10_2","doi-asserted-by":"publisher","DOI":"10.1021\/ar980117g"},{"key":"e_1_2_6_11_2","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3757(20010202)113:3<502::AID-ANGE502>3.0.CO;2-A"},{"key":"e_1_2_6_11_3","doi-asserted-by":"publisher","DOI":"10.1002\/1521-3773(20010202)40:3<486::AID-ANIE486>3.0.CO;2-P"},{"key":"e_1_2_6_12_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0010-8545(02)00256-4"},{"key":"e_1_2_6_13_2","doi-asserted-by":"publisher","DOI":"10.1039\/b411758a"},{"key":"e_1_2_6_14_2","doi-asserted-by":"publisher","DOI":"10.1002\/1099-0682(200010)2000:10<2143::AID-EJIC2143>3.0.CO;2-3"},{"key":"e_1_2_6_15_2","first-page":"117","volume-title":"Fluorescence of Supermolecules, Polymers, and Nanosystems, Springer Series on Fluorescence, Vol.\u20054","author":"Parola A. 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