Francesca Tancini's research while affiliated with Università di Parma and other places

Publications (15)

Article
A theoretical investigation based on DFT, TD-DFT, and CASSCF/CASPT2 methods has been carried out to elucidate the photophysics of two anilino-substituted pentacyano- and tetracyanobuta-1,3-dienes (PCBD and TCBD, respectively). These molecules exhibit exceptional electron-accepting properties but their effective use in multicomponent systems for pho...
Article
A variety of push–pull-chromophore–[60]fullerene conjugates connected with different spacers was successfully synthesized by applying “click chemistry” to the corresponding acetylene-appended fullerene precursors. Direct connection of the fullerene cages to push–pull motifs gives rise to ground state electronic interactions, which were characterize...
Article
The synthesis, electrochemical, and photophysical properties of five multicomponent systems featuring a Zn(II) porphyrin (ZnP) linked to one or two anilino donor-substituted pentacyano- (PCBD) or tetracyanobuta-1,3-dienes (TCBD), with and without an interchromophoric bridging spacer (S), are reported: ZnP-S-PCBD (1), ZnP-S-TCBD (2), ZnP-TCBD (3), Z...
Article
We describe the design, synthesis and conformational assignment of three diasteromeric bis-phosphonate cavitands based on an aryl extended calix[4]pyrrole tetrol scaffold. The diastereoisomers differ in the relative spatial orientation of the P═O groups installed at their upper rims. We demonstrate that these compounds act as heteroditopic receptor...
Article
Proacetylenic: An aniline-based donor-acceptor-substituted butatriene exhibits not only cumulene-like dimerization to give a [4]radialene (λ(max) =756 nm), but also acetylene-like (proacetylenic) reactivity towards tetracyanoethene, affording via [2+2] cycloaddition-cycloreversion a NIR-absorbing zwitterionic chromophore (λ(max) =825 nm). The catio...
Article
We report the synthesis and physical study of a series of 1,1-dicyano-4-[4-(diethylamino)phenyl]buta-1,3-dienes in which the number and position of additional CN substituents along the 1,1-dicyanobuta-1,3-dienyl fragment is systematically varied. While X-ray analysis provided unambiguous information about molecular geometries in the crystal, UV/Vis...
Chapter
IntroductionCavitandsSelf-Assembly of Ditopic Cavitand MonomersConclusions and OutlookReferences
Article
The outstanding complexing properties of tetraphosphonate cavitands towards N-methylpyridinium salts were exploited to realise a new class of linear and cyclic AABB supramolecular polymers through host-guest interactions. The effectiveness of the selected self-association processes was tested by (1)H NMR studies, whereas microcalorimetric analyses...
Article
The capability of resorcinarenes to bind anions within the alkyl feet at the lower rim has been exploited as the starting point for developing a new cavitand able to engulf contact ion pairs of primary ammonium salts in chlorinated solvents with association constants (K(ass)) in the range of 10(3)-10(4) M(-1). Methylene bridges were introduced into...
Article
A set of modular components was designed, synthesized, and combined to yield an innovative, robust, and reliable methodology for the self-assembly of large supramolecular structures on silicon wafers. Specific host-guest and H-bonding motifs were embedded in a single molecule by exploiting the remarkable complexing properties of tetraphosphonate ca...
Article
Quinoxaline kite velcrands were functionalized with a ureidopyrimidone moiety at the lower rim, in order to combine multiple hydrogen bonding and solvophobic interactions to build dual-coded supramolecular structures. The orthogonality of the selected binding motifs has been demonstrated by NMR studies, as well as the reversible nature of the obtai...
Article
The phosphorus-bridged cavitand 1 self-assembles very efficiently in CH2Cl2 with either the monopyridinium guest 2+ or the bispyridinium guest 3(2+). In the first case a 1:1 complex is obtained, whereas in the second case both 1:1 and 2:1 host-guest complexes are observed. The association between 1 and either one of the guests causes the quenching...
Article
Supramolekulare Plastizität: Die bemerkenswerte Wirt-Gast-Chemie von Phosphonatcavitanden wurde zum Aufbau selbstorganisierter supramolekularer Polymere genutzt (siehe Bild), die reversibel auf die Bindung von Gastspezies hin entstehen und je nach Templat von der linearen in eine sternförmig verzweigte Form wechseln. Ein Thiophosphonatcavitand mit...

Citations

... [14][15][16][17][18] In contrast, the luminescence properties of TCBD derivatives have barely been explored as they are generally considered non-emissive due to intrinsically rapid nonradiative deactivations. [19] However, some examples of luminescent TCBDs in solution or in the solid state have recently emerged, [20][21][22][23][24][25][26][27][28][29][30][31][32][33][34] although often with very low quantum yields at room temperature that hardly exceed 1 %, except for a work from Jayamurugan et al. [27] where the authors claimed quantum yields up to 4.3 % at room temperature in acetonitrile. We also reported TCBDs bearing triphenylamine and fluorenyl units that showed quantum yields comprised between 2 and 6 % in rigid media at room temperature. ...
... It is expected that ring X is positioned parallel to the fullerene surface in order to prevent steric repulsion between the aromatic protons of the ring and the fullerene surface.T his hypothesis is in keeping with the results of crystallographic analyses of relevant pyrrolidinofullerenes. [20] Moreover,N ierengarten and co-workers reported that rotation around the phenyl-pyrrolidine bond in phenyl-substituted pyrrolidinofullerenes is restricted. [21] Theneighboring ring, that is,ring Y,ispreferentially perpendicular to ring X,owing to the steric repulsion between the aryl protons.Accordingly, it is expected that the organic moiety,R ,w hich is connected with ring Y through an ester linkage,b ecomes close to the fullerene surface in the folded conformation, in am anner similar to that for the folded conformation of the Wilcoxs torsion balance.O nt he other hand, it is likely that Rw ould move away from the fullerene surface in the unfolded conformation. ...
... According to Anderson (2007), discriminant analysis is least used in credit scoring because of its likelihood of classification errors when predicting categories. Perhaps the oldest model used for credit scoring is probit regression, which was applied in 1934 by Chester Bliss (Abbott, 2014). ...
... [4] Per se, TCBDs are powerful electron acceptors, which are easily integrated on activated alkynes through a [2 + 2] cycloaddition-retroelectrocyclization (CA-RE) reaction with tetracyanoethylene (TCE). [5] As a consequence, TCBDs have been combined with, for example, triphenylamine, [6][7][8] BODIPY, [9,10] truxenes, [11] fullerenes, [12] corannulenes, [13] (sub)porphyrins, [14][15][16][17] and (sub) phthalocyanines [18][19][20][21][22] towards the realization of DÀ A conjugates. Next to being an outstanding electron acceptor, the TCBD structure is peculiar owing to the quasi-orthogonal arrangement of its two dicyanovinyl (DCV) halves [5] and the restricted rotation around the CÀ C bond connecting them. ...
... Recently, new studies on supramolecular polymers have started to exploit host-guest interactions designing systems with cyclodextrins, 11 cucurbiturils, 12 pillararenes, 13 calixarenes 14,15 and cavitands [16][17][18] as receptors. Among these, systems based on tetraphosphonate cavitands with their allinward configuration and ammonium salts proved to be suitable monomers for new supramolecular polymers 19,20 and for polymer blending 21,22 because of their outstanding complexation properties and high association constants. ...
... The initial upfield shifts observed for the TBA + alpha methylene protons, located the TBA + cation of the 1:1:1 ion-paired complex, Cl − •2Au•TBA + , in the shallow and electron rich cavity defined by the pyrrole rings of the receptor's cone conformation. This cavity is opposite to the binding site of the chloride resulting in a receptor-separated binding geometry for the ion paired complex, Cl − •2Au•TBA + [10,21,22]. During the titration, the overall concentration of TBACl is increased favoring the relative amount of free salt. ...
... This method takes advantage of the ability shown by tetraphosphonate cavitands to selec- tively recognize the + NH 2 -CH 3 group ( + NHR-CH 3 in the case of cocaine) common to all the above-mentioned drug salts through the concomitant formation of CH 3 Á Á Á inter- actions and hydrogen bonding. Indeed, resorcinarene-based cavitands (Cram, 1983;Cram & Cram, 1994) decorated at the upper rim with phosphonate groups or quinoxaline moieties have long been exploited for their molecular recognition properties towards charged and neutral molecules (Dutasta, 2004;Vachon et al., 2011;Melegari et al., 2013;Pinalli et al., 2016;Tudisco et al., 2016;Trzcin´skiTrzcin´Trzcin´ski et al., 2017;Pinalli et al., 2018;Wu et al., 2012;Clé ment et al., 2015). In order to further assess the recognition properties of tetraphosphonate cavi- tands towards quaternary ammonium salts of social interest, the supramolecular complex between Tiiii[C 3 H 7 , CH 3 , C 6 H 5 ] and mephedrone hydrochloride is herein reported and analysed, both in the solid state through the detailed analysis of its crystal and molecular structure, and in solution via NMR studies. ...
... Most of the ester derivatives presented in this article were known and synthesized before by other groups (1a-1j, 2a-2j and 3a-3e) [19,[31][32][33][34][35][36][37][38][39][40][41][42][43]; however, most of them were never tested as plant resistance inducers (except 3a-3c that were patented as SAR inducers) [19]. Besides the substances mentioned above, we have prepared one new ester (3f) and two new diester derivatives (3i, 3j) of 2,6-dichloroisonicotinic acid ( Figure 1) and reported the synthesis, characterization, and biological properties. ...
... Nevertheless, the phase transitions seem to be reversible. The melting point of N-octylammonium bromide is described in the literature with 408-409 K (207-208 • C[291]) and can be excluded to be present in this measurement. ...
... However, a versatility of polymeric supports have been reported; some of them toil from one or more faults in their attributes or synthetic ways, including multiplex steps for synthesis, long reaction times, rude reaction status, the utilization of costly catalysts and solvability in different solvents and low chemical and/or thermal stability. In view of the easiness of provision and the unique properties of the network polycalix [4] resorcinarene (PC4RA), such as multifaceted chemical rectification, good dispersion of active sites, its outspoken functionalization way via post-functionalization without undergoing copolymerization or further post-polymerization, porous surface and high chemical and thermal stability, it would be rational to consider this polymeric structure as a promising starting substance for the synthesis of a new and effective porous organic polymer [13][14][15][16][17][18][19][20][21][22][23][24][25][26]. To the best of our scholarship, in spite of many progresses in the plan, synthesis and usage of functionalized C4RA, there have been no reports on its functionalization through covalently anchored metalloporphyrin onto the overhead rim of C4RA. ...