The Discovery of the Fullerenes or “When Harry met Michael”

Martha Jura

Simon Balm Santa Monica College Several Aspects and Agendas

1) To describe the intersecting careers of a chemist, Harry Kroto in England, and an astrophysicist, Michael Jura in California. 2) To bring focus on a pivotal event in the discovery of the Fullerenes, which occurred in 1989, midway between Harry’s Nature Paper (1985) proposing Buckminsterfullerene and his receipt of the Nobel Prize (1996). 3) To discuss the influence of the work of Harry and Michael on the eventual discovery of Fullerenes in space. Between the Nature paper in 1985 and the Nobel Prize in 1996: the Krätschmer paper

• We have been asked to describe a mere moment in scientific history, when a small deal turned out to be a big deal. • In 1989 Michael sent a paper by the Krätschmer group to Harry in Sussex from a conference in Capri.

• This knowledge started a race to isolate C60 and led to the confirmation of its controversial structure. • This event occurred in the context of an ongoing friendship between two scientists who respected and liked each other. For Reference: Some Important Dates

• 1985: Harry and co-authors first describe C60 as Buckminsterfullerene in a Nature paper. C60 first predicted to be in the interstellar medium. + • 1987: Harry suggests C60 might be a carrier of some of the diffuse interstellar bands. • 1989: Michael sends the Krätschmer paper to Harry, suggesting that macroscopic quantities of C60 can be formed and isolated in the lab.

• 1990: C60 isolated from soot and structure confirmed. • 1992: paper published by Michael and Harry on fullerenes in space. • 1996 when Harry and colleagues received the Nobel Prize for their work on the Fullerenes.

• 2010: neutral C60 found in space by Spitzer. + • 2015: two diffuse interstellar bands assigned to C60 Before and After the Krätschmer Paper

• Harry’s Nature paper describing C60 as a Buckyball was not universally well received. • Michael and Harry described the period between 1985 and 1989 as the “Dark Times,” when Harry and his colleagues were maligned and attacked. • As Simon was working with Harry as a graduate student at the time, he can describe being confronted when presenting results based on the work of Harry’s lab on C60. • Everything changed when Michael sent the Krätschmer paper to Harry. Two Eye-Witness Accounts around the Krätschmer Paper, 1989 • Martha was with Michael when he sent the paper to Harry from Capri. • Simon was with Harry when he received the paper in Sussex. • So we have two eye-witness accounts from the sending and receiving end of this event. The Paper Facilitated Harry’s Work on C60

• The Krätschmer paper was vital in alerting Harry to the fact that despite previous attempts, C60 could be produced in macroscopic quantities, isolated and therefore the proposed structure confirmed.

• Simon will speak to the impact of Krätschmer’s findings, and their importance to Harry’s work.

• Since Simon worked with Harry as a graduate student in the late 80’s and with Michael as a postdoc in early 90’s, he is in a position to describe not only their work but their relationship. Laser Vaporization Cluster Beam System

Rick Smalley, Rice University

Designed to study the clustering of refractory elements in the gas-phase

Chains C60 A 60-atom Graphite Fragment Richard Buckminster Fuller’s Expo ‘67 Dome Pentagons produce Curvature C60: Buckminsterfullerene

Truncated Icosohedron C70 The “Lone Ranger” and “Tonto” Rick Smalley, Bob Curl and Harry with grade Students Jim Heath and Sean O’Brien

Nature 318, 162 - 163 (14 November 1985) Harry Kroto, Simon Balm and Wahab Allaf at Sussex in the late 1980’s

Fullerene hypothesis very controversial

Needed to make enough C60 in order to characterize it Attempts to extract C60 from samples collected by cluster beam technique failed Donald Huffman (UofA) and Wolfgang Krätschmer (MPIK) The Capri Paper of September 1989 that Michael sent to Harry

Dusty Objects in the Universe, Workshop of the Astronomical Observatory of Capodimonte Held in Capri, Italy, September 8–13, 1989 NOVA Documentary “Race to Catch a Buckyball” (1995) The Red Vial containing C60 made at Sussex 5 days before Krätchmer’s Nature paper was sent to Harry to referee in August 1990

13C Nuclear Magnetic Resonance Spectra of Complex Molecules

Separate peak for each carbon atom in a unique electronic environment 13 C Nuclear Magnetic Resonance Spectrum of C60

Even through C60 has 60-atoms they are identical and so only a single peak!

Isolation, separation and characterisation of the Fullerenes C60 and C70; the third form of carbon J. Chem. Soc. Chem.,Commun., 1423-1425 (1990) Harry wins the 1996 Nobel Prize in Chemistry with Smalley and Curl Fullerenes in Space?

Resistant to Photodissociation

NOVA Documentary “Race to Catch a Buckyball” (1995)

Inconclusive identifications due to matrix shifts

Michael and Harry: Colleagues and Friends

NASA Workshop on Isotopic Anomalies, Clemson University USA, November 1990