Appendix
Appendix I
Table 1: Summary of the most relevant applications of salen- and salophenmetal complexes in catalysis, NLO, formation of supramolecular assembly, etc: Metal (oxidation state), type of the ligand, function and referenceMetal (ox. state) / Ligand type / function / Ref.
Ni (II) / Salen / DNA modification with KHSO5 / 1
Salen / Biotin-tag delivery into DNA structure / 2
Salen\salophen / NLO / 3
Fe (III) / salen / Artificial Metalloproteins
Interaction with native DNA / 4
5
Ru (II) / Salophen\salen / Catalyst for alcohol oxidation / 6
Salen\salophen / Photochemical nitric oxide release / 7
Mn (III, V) / Salen / Supramolecular assembly enhanced activity and stability / 8
Salen / Asymmetric epoxidation of olefines / 9
Salen\salophen / di--oxo model for Mn centre of PSII(OCE) / 10
Salen / Catalase mimic / 11
Salen / Oxidation of ketone sylil enol ethers to -hydroxy ketones / 12
Cr (III, V) / Salen / Asymmetric catalysis of epoxides ring opening / 13
Salen / Iodocyclization of -hydroxy cis alkenes / 14
Salen / Epoxidation of olefines / 15
Salen / Catalysis of Hetero-Diels-Alder / 16
continue…
…continue
Co(II, III) / Salen / Hydrolytic Kinetic Resolution of Terminal Epoxides / 17
Salen / Enantioselective epoxides ring opening with carboxylic acids / 18
Salen / Asymmetric cyclopropanation of styrene / 19
Salen / HKR of epoxides / 20
salen / asymmetric epoxides ring opening / 21
Al (III) / Salen / Stereocontrol in polymerisation of racemic lactide / 22
Salen / Enantioselective addition of HCN to imine (Strecker reaction) / 23
salen / Michael addition to ,-unsaturated imides / 24
Cu (II) / Salen / DNA cleavage / 25
Ti (IV) / Salen / Trimethylsylilcyanation of aldehydes / 26
Oxidation of sulphides / 27
Nb(IV, V)
Mo(II, IV)
Ti (II, III)
V (II, III) / salophen / Potential components of molecular batteries
Chem. Eur J. 1999 (24.pdf),25.pdf / 28
Zn (II) / salen / Chemo selective alkylation of -chetoesters / 29
salen / Neutral Carrier for Highly Selective PVC Membrane Sensors for the Sulphate Ion / 30
UO2 (VI) / See Sections 1.4, 2.2-2.7, 3.3-3.4, 4.2, 5.2.
References:
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Appendix II
1H-1H-ROESY experiment
Figure 1: 1H-1H-ROESY experiment between A and 19
Weak but real correlation spot is found at the intersection between the benzyl methylene signal of A and the trimethylammonium signal of the phophocholine 19 (red circle).
Appendix III
Instrumental and methods: NMR, UV-vis, SEM/EDS and X-rays.
NMR: 1D and 2D NMR techniques have been used to study association equilibria in solution (200, 250, 300 and 500 MHz spectrometers). Translation of the titration experiments into estimates of the binding constants K was straight-forward in most of the cases. Data could be fitted to a good precision to Equation 1, where the binding constant K the upfield shift ( referred as CIS in the text) of the guest fully saturated by the host and the guest chemical shift (o) in the absence of hostwere treated as adjustable parameters in a non-linear least-squares fitting procedure. When possible a multifit procedure was used. Increasing quantities of stock solution of salts were added to a weighted amount of host (1-5 mg). This procedure allows to maintain the concentration of the salt (usually ca. 5x10-4 M) constant, avoiding the formation of higher aggregates of ion-pairs. Temperature is maintained at 25°C.
/ Eq. 1Host concentration (Ho) is maintained in the range given in Equation 2. This procedure guarantees the best condition to measure the equilibrium constant (20-80% complexation).
/ Eq. 2UV-vis: APerkin Elmer Spectrometer was used in the spectroscopic titrations. All titration experiments were carried out at 25°C. Typical procedures of the titration experiments are as follows. Solvent (2 mL) was placed in a glass cell, and 10l-150l of stock solution of the host in the same solvent was added to the cell. Then the UVvis spectrum was recorded. A calculated amount of the guest stock solution in chloroform was added to the sample cell. The solution was stirred for 30s and the spectrum was recorded. Additional amounts of the guest stock solution were then added to the cell, and the spectrum was recorded after each addition. Titration data were fitted by 1:1 binding isotherm, whenever possible (Equation 3)
/ Eq. 3Binding constant K and the changes in the extinction coefficient were treated as adjustable parameters in the non-linear least-squares fitting procedure. When possible a multifit procedure was used.
SEM/EDS:Scanning electron microscope LEO1450VP and EDS analysis by INCA300. The sample was prepared as follows: an excess of alkali halide salt was added to a solution of the receptorin chloroform. After almost complete precipitation (the initial dark red solution becomes pale yellow) the solution was removed and the solid dried by vacuum. The image (with a resolution of 3.5 nm) is the result of the secondary electrons extracted from the sample by the principal electronic beam.
A control analysis has been also performed in order to test the effectiveness of the technique on a pure and homogeneous sample. CsCl has been analysed. Figure 2 shows an image of the sample along with the EDS spectrum. The elemental analysis perfectly matches the calculated data (50.13% Cs and 49.87 %for Cl).
Figure 2: Sem image and EDS analysis on pure CsCl.
X-rays Data Collection and Crystal Structure Determinations: X-rays data for all complexes were collected on a Nonius Kappa CCD diffractometer using graphite monochromatised MoK radiation and the temperature of 173.0 K. Structure solution was performed by SIR-92 or SHELXS-97 and refined on F2 by full-matrix leastsquares techniques (SHELXL-97). Hydrogen atoms were calculated to their idealised positions and refined as riding atoms (temperature factor 1.2 or 1.5 times C temperature factor). Absorption correction was applied to all structures.
Crystallographic details for the structures presented in Chapter 2 are reported in Table 2a and 3a.
Table 2a.A·TMACl / A·TBACl / B·TMACl / C·TMACl / B·AChCl
Formula / C34H26N2O6U· TMACl / 2C34H26N2O6U· 2 TBACl / 4C42H30N2O6U·5+1/3TMACl ·4+1/2MeCN / C20H14N2O4U· TMACl·1/3 MeCN / 2C42H30N2O6U· 2AChCl·4MeCN
Formula weight / 906.19 / 1074.51 / 4353.07 / 707.64 / 2249.95
Crystal system / Tetragonal / Triclinic / Trigonal / tetragonal / Triclinic
Space group / I-4 (No. 82) / P-1 (No. 2) / R 3c (No. 161) / R-3 (No. 14) / P-1 (No.2)
Crystal colour / red / Red / Orange / Red / red
a / Å / 19.293 / 13.3226 / 54.1597 / 22.5983 / 12.3021
b / Å / b=a / 18.2986 / b=a / b=a / 16.8778
c / Å / 19.421 / 20.3692 / 33.1332 / 15.5041 / 26.4855
/ ° / 90 / 94.6846 / 90 / 90 / 72.5610
β / ° / 90 / 104.4632 / 90 / 90 / 84.5141
/ ° / 90 / 91.9727 / 120 / 120 / 75.4356
V / Å3 / 7229 / 4783.23 / 8415.8 / 11380.73 / 5076.67
Z / 8 / 4 / 18 / 18 / 3
Final R indices / 0.0482/ 0.0577 / 0.040 / 0.0609 / 0.0451 /0.0657 / 0.038 / 0.083 / 0.0467/0.0641
Table 3a.
A·NMP I / A·NMDABCOCl / H·TMACl / J·TMACl / 8·NMQBr (Chapter 5)
Formula / C34H26N2O6U·NMPBr·MeCN / 2C34H26N2O6U· NMDABCOCl2·5MeCN / 4C36H30N2O8U·5+1/3TMACl ·4CHCl3 / C34H24N2O6UBr2·TMACl·1/8H2O / C32H22N2O10S2U· C8H16NBr
Formula weight / 1031.68 / 2003.5 / 4488.45 / 1026.75 / 1102.79
Crystal system / monoclinic / Monoclinic / trigonal / tetragonal / Monoclinic
Space group / C2c (No. 15) / P21/n (No. 14) / R 3c (No. 161) / I-4 (No. 82) / P 21/a (No. 14)
Crystal colour / Red / Red / Red / Orange / Orange
a / Å / 35.560 / 13.6586 / 53.381 / 19.6629 / 9.7511
b / Å / 9.6555 / 31.0969 / b=a / 19.6689 / 29.8731
c / Å / 24.1012 / 19.6726 / 32.715 / 19.5797 / 13.8492
/ ° / 90 / 90 / 90 / 90 / 90
β / ° / 112.379 / 93.0296 / 90 / 90 / 93.616
/ ° / 90 / 90 / 120 / 90 / 90
V / Å3 / 7650.9 / 8344.1 / 80734 / 7572.4 / 4026.18
Z / 4 / 2 / 18 / 2 / 4
Final R indices / 0.0729/ 0.1126 / 0.0451/ 0.0759 / 0.0653/0.1040 / 0.0301 / 0.0382 / 0.0518
Crystallographic details for the structures presented in Chapter 3 are reported in Table 4a.
Table 4a.A·CsF / A·CsCl / A·RbCl / A·KCl /
F·CsCl
Formula / C34H26N2O6U ·CsF·2CH3CN / C34H26N2O6U ·CsCl·2CH3CN / C34H26N2O6U ·RbCl·2CH3CN· 0.25H2O / 2C34H26N2O6U ·KCl·2CH3OH / 2C27H20N2O5U ·CsCl·2CH3CN·CH3OH · H2OFormula weight / 1030.62 / 1047.07 / 1004.15 / 1731.83 / 1681.51
Crystal system / monoclinic / triclinic / triclinic / triclinic / monoclinic
Space group / P21/n (No. 14) / P-1 (No. 2) / P-1 (No. 2) / P-1 (No. 2) / C2/c (No.15)
Crystal colour / red / red / orange / red / red
a / Å / 16.3779(7) / 12.0338(3) / 11.8754(4) / 14.3905(2) / 32.4597(7)
b / Å / 13.9653(6) / 12.3620(3) / 12.2205(5) / 15.2086(3) / 15.9145(4)
c / Å / 16.6928(5) / 14.5835(5) / 14.6154(7) / 15.5041(3) / 26.1849(4)
/ ° / 90 / 108.135(2) / 107.790(2) / 93.258(1) / 90
β / ° / 107.568(2) / 97.069(1) / 96.735(2) / 107.142(1) / 120.983(1)
/ ° / 90 / 108.179(2) / 108.296(2) / 100.843(1) / 90
V / Å3 / 3639.9(2) / 1899.66(9) / 1863.4(1) / 3161.7(1) / 11596.6(4)
Z / 4 / 2 / 2 / 2 / 8
Final R indices / 0.027 / 0.062 / 0.052 / 0.096 / 0.058 / 0.140 / 0.038 / 0.083 / 0.034 / 0.076
GOF / 1.190 / 1.065 / 1.088 / 1.125 / 1.087
Appendix IV
Structural analysis of the complexes between H and J with TMACl.
Figure 3: a) H-TMACl 4:4 assembly and b) cutaway view showing the four TMACl guests inside the solid state assembly; c) J-TMACl 4:4 complex and d) view of the internal structure.
The two solid structures have similar features. They both from a 4:4 assembly, but a higher symmetry was found for the J-complex. In Table 5 and in Table 6 some of the most relevant intermolecular TMA methyl to aromatic carbon distances are given. Shorter contacts are found in H-TMACl (3.437 Å the shortest) compared to J-TMACl.
Table 5a: Relevant methyl to aromatic carbon distances (Å) for H-TMACl complexSet of interactions / Ring C / Ring A / Ring B
I
/ C1 4.414 / C17 3.909 / C33 3.841C2 4.966 / C18 3.933 / C34 3.437
C3 5.06 / C19 3.826 / C35 3.888
C4 4.772 / C20 3.651 / C36 4.630
C5 4.239 / C21 3.655 / C37 4.965
C6 4.006 / C22 3.748 / C38 4.538
II / C1 3.917 / C17 3.861 / C33 4.057
C2 4.125 / C18 3.462 / C34 3.788
C3 4.04 / C19 4.037 / C35 3.738
C4 3.748 / C20 4.757 / C36 3.737
C5 3.47 / C21 5.071 / C37 3.985
C6 3.551 / C22 4.654 / C38 4.092
III / C1 4.000 / C17 4.056 / C33 3.821
C2 3.742 / C18 3.85 / C34 3.688
C3 3.511 / C19 3.662 / C35 3.593
C4 3.564 / C20 3.715 / C36 3.628
C5 3.843 / C21 3.914 / C37 3.772
C6 4.022 / C22 4.071 / C38 3.82
Table 6a: Relevant methyl to aromatic carbon distances (Å) for J-TMACl complex
Ring A / Ring B / Ring C
C17 3.779 / C33 4.106 / C1 4.101
C18 4.235 / C34 4.03 / C2 4.061
C19 4.519 / C35 3.837 / C3 3.766
C20 4.363 / C36 3.677 / C4 3.546
C21 3.92 / C37 3.748 / C5 3.601
C22 3.599 / C38 3.966 / C6 3.865
Appendix V
Titration of 19 with receptor C.
Figure 5: Titration of 19 with host C. Data profile and portion of the relevant parts of the NMR spectra.
In effect the titration profile can be divided into three different regions (Figure 5). Starting from the host excess region, the first part () consists in a plateau. The guest’s signal does not change in this region. On the contrary host iminic signals shows two species in slow equilibrium (inset 1). Host A and B did not show such behaviour in the same condition: i.e. the host signals were not discriminated on the NMR time scale during the titration experiments. The second region () consists in the shift of the guest signal until the equivalence (inset 2) After this point the guest signals split into two, () whose relative intensity changes going further in the titration (inset 3). Since in this case there is no clear reason to suspect the binding ability of C to be greater than for A and B (they do not show this behaviour) we have to find a rationale. Indeed, generally a weaker association unlikely results in a slower exchange rate and vice versa. A hypothesis which takes into account a second weaker association equilibrium between host C and the esteric carbonyl of the guest might be considered, having in mind that salophen-uranyl compounds are known to weakly bind to enones. This second equilibrium would be active in the region where the host is in excess and the principal strong binding to the phosphoric moiety is already concluded and would be slow on the NMR time scale.
Appendix VI
KCl complex of A. There are similarities, but also significant differences between the solid state structure of the KCl·1 complex and those of the corresponding complexes of rubidium and cesium. The asymmetric unit contains a 1:1 complex, which forms 2:2 dimers similar to the largeralkali metals, but additionally there is another ligand with solvent methanol coordinated to the UO2 center in the crystal lattice (Figure 6).
This MeOH coordinated ligand is placed in between dimeric assemblies via edge-to-face and face-to-face interactions between the aromatic units of the ligand molecule (Figure 7). The role as well as the reason for the crystallization of the additional MeOH coordinated ligand is unclear. It is possibly related to the fact that the crystallization solvent used in this case was MeOH/H2O, while other complexes were obtained from CHCl3/MeOH/MeCN mixtures, but the operation of closest packing effects cannot be excluded. The structure of the dimeric potassium complex resembles closely the structures of the corresponding rubidium and cesium complexes (Figure 18, Chapter 3).
MeCN and MeOH Complexes of A. The structure of A·MeCN and A·MeOH complexes are not only interesting in their own rights, but also in connection with the question of why the complexation of the smallest alkali metal ions Li+ and Na+ was not successful. Both acetonitrile and methanol are bound to the uranyl center in the equatorial plane (Figure 8) and crystallise with similar unit cells and isomorphous structures despite of their different size. In the acetonitrile complex the sidearms of A are turned inward in a quasimacrocyclic conformation which fully encloses a CH···(3.63 Å) bonded CH3CN molecule.Corroborating evidence comes from the observation that A and CH3CN form a complex of definite stability in CDCl3 solution (K = 23 5 M-1, 25°C). The upfield shift suffered by the 1H NMR signal of MeCN upon complexation (-∞ = 0.06 ppm) demonstrates that the methyl group is under the influence of the ring currents of the aromatic walls and provides a strong indication that the structure of the complex in solution closely resembles the molecular structure in the solid state.
Unlike acetonitrile, the hosted methanol molecule is too small to fill the cavity completely and therefore is disordered over two positions inside the quasimacrocyclic cavity, where very weak C-H···π interactions (3.88 Å) between the hosted methanol and one of the aromatic side arms are established in each orientation. It is of interest to compare the structure of A·MeOH in Figure 8 with the structure of the methanol-coordinated A crystallized with KCl (Figure 6). In the latter, the aromatic sidearms do not interact with methanol at all, but are turned away to interact with aromatic parts of nearby receptors. It appears therefore that CH··· interactions with the unsuitably sized methanol are not strong enough to keep the quasimacrocyclic conformation as the most stable arrangement in all cases.
The difference in -interactions with the complexed solvent molecules emphasizes the significance of guest size for effective binding through -interactions. It seems therefore likely that, in spite of its high flexibility, receptor A is not geometrically suited to provide the smallest Li+ and Na+ cations with a favourable environment made up of a suitable pseudocrown ether arrangement and aromatic sidearms available for cation- interactions.
Crystal structures of solvent-receptor complexes of C. Numerous crystallisation experiments of receptor C with alkali metal salts resulted in only crystal structures of solvent-ligand complexes or powder-like precipitates unsuitable for crystal structure determination. This indicates clearly the significance of aromatic sidearms for alkali metal binding. Two different solvent-ligand structures are reported here in Figure 9.
Figure 9. Above: crystal structure of receptor C crystallised from MeOH:chloroform. Asymmetric unit contains two receptors, one of which coordinates methanol and another one with water. A disordered methanol and chloroform occupying the interstice in the crystal lattice are excluded for clarity. Below: crystallization of receptor C in MeOH:chloroform:acetonitrile resulted in the structure of receptor with coordinated acetonitrile.
Crystallographic details for the structures presented in this Appendix are reported in Table 7a.
Table 7°.A·MeCN / A·MeOH / C·MeOH / C·H2O / C·MeCN
Formula / C34H26N2O6U· ·CH3CN / C34H26N2O6U· ·CH3OH / [C20H14N2O4U ·CH3OH]· [C20H14N2O4U ·H2O]· CHCl3 / C20H14N2O4U·
CH3CN
Crystallization solvent mixture / CHCl3:MeCN: MeOH=1:2:1 / MeOH:CHCl3 =2:1 / CHCl3:MeOH=1:2 / CHCl3:MeCN: MeOH=1:1:1
Formula weight / 837.65 / 828.64 / 1368.18 / 625.42
Crystal system / orthorhombic / orthorhombic / triclinic / orthorhombic
Space group / Pnam (No. 62) / Pnam (No. 62) / P-1 (No.2) / Ccm21 (No. 36)
Crystal colour / red / orange / red / orange
a / Å / 9.6034(1) / 9.5634(2) / 12.5316(5) / 12.5727(5)
b / Å / 13.3230(2) / 13.7333(4) / 13.5637(4) / 16.8834(8)
c / Å / 23.3439(3) / 22.4731(7) / 13.9037(5) / 9.4729(3)
/ ° / 90 / 90 / 99.611(2) / 90
β / ° / 90 / 90 / 101.620(2) / 90
/ ° / 90 / 90 / 91.385(2) / 90
V / Å3 / 2986.76(7) / 2951.6(1) / 2278.3(1) / 2012.1(1)
Z / 4 / 4 / 2 / 4
Final R indices* / 0.017 / 0.038 / 0.042 / 0.095 / 0.040 / 0.096 / 0.020 / 0.041
GOF / 1.111 / 1.105 / 0.981 / 1.082
1