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.

Marriage Certificate - Charles Nickles & Margaret Nelles

A marriage license for "Charles Nickles of the Township of Grimsby Gentleman and Margaret Nelles of Same place Spinster" and is dated 23 July, 1831.

Entrance Examination Certificate Collegiate Institutes and High Schools of Ontario - Mary Willson

A certificate from the Collegiate Institutes and High Schools of Ontario of the Education Department of Ontario stating: "It is hereby certified that Mary Willson has passed the entrance examination required by the Education Department for admission to a Collegiate Institute or High School. Dated at Welland August 1st, 1908. Signed John W. Marshall, B.A. Inspector of Public Schools.

Certificate of Acceptance and Initiation to Canadian Order Chosen Friends - Thomas Cowan

A certificate of initiation and acceptance to the Canadian Order Chosen Friends, Thomas Cowan. The certificate reads "This certifies that evidence has been received that Thomas Cowan has been accepted and initiated by the Council name below, and has thus become a member of the Canadian Order of Chosen Friends, and entitled to all the rights and privileges of membership and a benefit of not exceeding one thousand dollars from the relief fund of said order, which shall in case of death be paid to Annie Cowan his wife in the manner and subject to the conditions set forth in the laws governing said relief fund and in the application for membership. This certificate to be in force and binding when accepted in writing by the said member, with the acceptance attested by the Councilor and Recorder and the seal of the Subordinate Council affixed, so long as said member shall comply with the requirements of the Constitution, Laws and Regulations now in force or hereafter adopted for the government of the Order: otherwise, and also in the case of granting of a new certificate, to be null and void. In witness whereof, we have hereunto attached our signatures, and affixed the seal of the Grand Council of the Canadian Order of Chosen Friends. Dated the Twenty Seventh day of July, A.D. 1891." The front and back of the certificate are available for viewing.

Certificate of Membership United Empire Loyalists Association of Canada

A certificate that Francis Bond Head Wilson "being of United Empire Loyalist Descent has been regularly proposed, balloted for, and elected a member of this association." It is dated September 14th, 1934.

Marriage Certificate - Thomas Cowan & Annie Easling, 1884

A marriage certificate for Thomas Cowan of Thorold and Annie Easling of St. Catharines. The certificate is dated October 8, 1884 and is witnessed by W. Ross and Jennie McElroy.

Shares Certificate - Gladstone Mines and Reduction Company

A shares certificate for Gladstone Mines and Reduction Company in the amount of 200 shares. The certificate is dated 13 March 1925 and is signed by the secretary F.J. Carr and the president Charles Stoddart. The price is one dollar per share and it is made out to W.H. Cowan.

Certificate of Service

A certificate of service detailing the career of Lieut.-Colonel Frank Case McCordick. He is noted at being enlisted in the 19th Battalion on the 13th November, 1914. He served in Canada, England and France and was "struck off the strength" November 21, 1918. The certificate is dated 16 October, 1919.

Communion Certificate - Helen Stanley Smith, 1919

A communion certificate for Helen Stanley Smith dated 31 January, 1919. The certificate is signed by George H. Smith D.D. (minister).

Girl Guides Certificate, 1915

A certificate enrolling Helen Smith as a B.P. Girl Guide, 2nd Company, 17 June 1915. Three proficiency badges are marked off as achieved.

Canadian Army Certificate of Service

A certificate of service from the Canadian Army for Lt. Col. Frank Edward McCordick. The document describes where he served (United Kingdom, Central Mediterranean, Continental Europe) and the length of his service (1939-1945). Included on the certificate is a list of medals/decorations which include: 1939-45 Star, Italy Star, France and Germany Star, Defence Medal Canadian Volunteer Service Medal and Clasp.

Certificate of Honour

A certificate of honour for Frank E. McCordick, dated 6th September, 1945. The certificate was awarded to McCordick for recognition of his service during World War II.

Catherine Everingham land grant, 1802 [photocopy]

Catherine (Lemon) Everingham was the widow of James Everingham, a private with the first Battalion of Colo Delancys Regt. of the Jersey Volunteers. He died in the American Revolutionary War in 1796, leaving his wife and two children settled on two hundred acres of land in the Township of Willoughby. No certificate had been awarded to James Everingham for this land. Catherine subsequently petitioned the government to grant her the land that she had settled on with her family.

100th Birthday Certificate, 2011

A certificate of congratulations of the occasion of Dorothy Rungeling's 100th birthday, 12 May 2011. There is a certificate of best wishes signed by Prime Minister Stephen Harper and a certificate from the House of Commons Canada signed by Dean Allison, Mp Niagara West-Glanbrook.

Cuban Tourist Commission Air Certificate, 1955

A certificate from the Cuban Tourist Commission "in recognition of his success in crossing the Channel to Cuba from the United States in the Sixth Annual All Women International Air Race". The certificate was awarded to Dorothy Rungeling on July 11, 1955.