The Synthesis and Coordination Chemistry of Two Families of Polydentate Ligands - Exploring Their Potential for the Preparation of Molecule-Based Magnets

The synthesis and studies of two classes of poly dentate ligands are presented as two projects. In project 1, four new carboxamide ligands have been synthesised via the condensation of 2,2',6,6'-tetrachloroformyl-4,4'-bipyridine or 2,6-dichloroformyl pyridine together with heterocyclic amines containing pyridine or pyrazole substituents. The coordination chemistry of these ligands has been investigated and studies have shown that with a Cu(II) salt, two carboxamide ligands LJ and L2 afford large clusters with stoichiometries [Cu8(L1)4Cl16].CHCl3.5H2O.7CH3OH (I) and [Cu9(L2)6Cl6].CH3OH.5H2O.(C2H5)3N (II) respectively. [molecular diagram availabel in pdf]. X-ray diffraction studies of cluster (I) reveal that it has approximate S4 symmetry and is comprised of four ligands and eight copper (II) centers. Here, coordination takes place via amide 0 atoms, and pyrazole nitrogens. This complex is the first reported example of an octanuclear copper cluster with a saddle-shaped structure. The second cluster comprises nine copper ions that are arranged in a cyclic array. Each ligand coordinates three copper centers and each copper ion shares two ligands to connect six ligands with nine copper ions. The amide nitrogens are completely deprotonated and both amide Nand 0 atoms coordinate the metal centres. The cluster has three-fold symmetry. There are six chloride ions, three of which are bridging two neighbouring Cu(II) centres. Magnetic studies of (I) and (II) reveal that both clusters display weak antiferromagnetic interactions between neighbouring Cu(II) centers at low temperature. In the second project, three complexes with stoichiometries [Fe[N302](SCN)2]2 (III), R,R-[Fe[N3O2](SCN)2 (IV) and R,R-]Fe[N3O2](CN)2] (V) were prepared and characterized, where [N302] is a pentadentate macrocycle. Complex (III) was prepared via the metal templated Schiff-base condensation of 2,2',6,6'-tetraacetyl-4,4'-bipyridine together with 3,6-dioxaoctane-I,8-diamine and comprises of a dimeric macro cycle where the two Fe(II) centres are in a pentagonal-bipyramidal environment with the [N302] ligands occupying the equatorial plane and two axial NCS ligands. Complexes (IV) and (V) were prepared via the condensation of 2,6-diacetylpyridine together with a chiral diamine in the presence of FeCh. The synthetic strategy for the preparation of the chiral diamine (4R,5R)-4,5-diphenyl-3,6-dioxa-I,8-octane-diamine was elucidated. The chirality of both macrocycles (IV) and (V) was probed by circular dichroism spectroscopy. The crystal structure of (IV) at 200 K contains two independent molecules in the unit cell, both of which contain a hepta-coordinated Fe(II) and axial NCS ligands. Variable temperature magnetic susceptibility and structural studies are consistent with a high spin Fe(II) complex and show no evidence of any spin crossover behaviour. In contrast, the bis cyanide derivative (V) crystallizes with two independent molecules in the unit cell, both of which have different coordination geometries consistent with different spin states for the two Fe(II) centres. At 250 K, the molecular structure of (V) shows the presence of both 7- and a 6-coordinate Fe(II) complexes in the crystal lattice. As the temperature is lowered, the molecules undergo a structural change and at 100 K the structural data is consistent with a 6- and 5-coordinate Fe(II) complex in the unit cell. Magnetic studies confirm that this complex undergoes a gradual, thermal, spin crossover transition in the solid state. Photomagnetic measurements indicate this is the first chiral Fe (II) sea complex to exhibit a LIESST.

Second interim report of the Canadian section and first joint report of the International Waterways Commission (1906)

Report of the Canadian section, dated April 25th, 1906, and report of the joint commission, dated May 3d, 1906, related to regulating the uses of the waters of the Niagara River and the preservation of the Falls.

Erie & Niagara Railway Collection, 1864-1884

William Alexander Thomson (1816-1878) was a promoter and developer of railway systems in western Ontario. He incorporated the Fort Erie Railroad Company in 1857, purchased the Erie and Ontario Railroad in 1863, and incorporated the Erie and Niagara Extension Railway Company in 1868 (later renamed the Canada Southern Railway). Thomson was also elected to the House of Commons for Welland in 1872, and re-elected in 1874. He was known for his support of public management of the currency and is seen as a pioneer advocate of government monetary policy. He was also an advocate of radical agrarian economic doctrine, believing that Canadian laws favoured mercantile interests over those of the producers of goods, and that this hindered national development.

Calculations regarding quantities needed for cutting and ditching

Calculations regarding quantities needed for cutting and ditching (1 page, handwritten), March 19, 1884.

Memorandum of expenses for work done and materials provided by Messrs. Brown and McDonell

Memorandum of expenses for work done and materials provided by Messrs. Brown and McDonell, contractors for the Port Dalhousie and Thorold Railway to Sept. 1, 1854, signed by S.D. Woodruff, Sept. 2, 1854.

Memorandum of material furnished for superstructure on the line of the Port Dalhousie Thorold Railway by contract

Memorandum of material furnished for superstructure on the line of the Port Dalhousie Thorold Railway by contract. This document includes: Bills of timber, memorandums of planking, fencing, ties, track laying, masonry and bolts and spikes. There are also diagrams of culverts. One of the pages is loose and the outer pages are somewhat discoloured (32 pages, handwritten and bound with ribbon, n.d.

Memorandum respecting differences between the approximate and the final estimate

Memorandum respecting differences between the approximate and the final estimate (3 ¼ pages, handwritten), n.d.

List of the number of loads dredged by Smiley’s Dredge since the 1st of October along the Welland Railway

List of the number of loads dredged by Smiley’s Dredge since the 1st of October along the Welland Railway. This is addressed to S.D. Woodruff and signed by James Woodall of Lock No. 1. There are holes and stains in the document. Text is not affected, Jan. 12, 1859.

Diagrams of cross sections on the Welland Railway, Port Dalhousie

Diagrams of cross sections on the Welland Railway, Port Dalhousie (4 hand-drawn diagrams), March 1860.

Scrap of paper with numbers of railway journals volume numbers, n.d.

Scrap of paper with numbers of railway journals volume numbers, n.d.

Amount paid to Frederick Holmes by the Welland Railway Company

Amount paid to Frederick Holmes by the Welland Railway Company for 26 days of service during February, March and April for excavations made at Port Dalhousie (1 page, handwritten). This is signed by S.D. Woodruff, Aug. 28, 1860.

Voucher #22 to James McCoppen (copy) which includes a letter from James McCoppen regarding a claim for having water backed up into his grain and grass by the embankment of the railroad. The letter is dated June 24, 1857 and the voucher is dated Jul. 1, 1857

Voucher #22 to James McCoppen (copy) which includes a letter from James McCoppen regarding a claim for having water backed up into his grain and grass by the embankment of the railroad. The letter is dated June 24, 1857 and the voucher is dated Jul. 1, 1857.

Pay roll voucher #27 from the Engineer Department of the Welland Railway for sundries for the month of August, 1857. A section of the list has been cut from the page, Aug. 31, 1857

Pay roll voucher #27 from the Engineer Department of the Welland Railway for sundries for the month of August, 1857. A section of the list has been cut from the page, Aug. 31, 1857.

Pay roll voucher #30 from the Engineer Department of the Welland Railway for the Southern Division for the month of August, Aug. 31, 1857

Pay roll voucher #30 from the Engineer Department of the Welland Railway for the Southern Division for the month of August, Aug. 31, 1857.

Letter to W.D. Woodruff from E.C. Wheeler Jr. of N.W. Harris and Co. Bankers of New York

Letter to W.D. Woodruff from E.C. Wheeler Jr. of N.W. Harris and Co. Bankers of New York (1 page, printed) regarding taking on some more of the Chicago, Rock Island and Pacific Railway bonds, Jan. 15, 1909.